Host–Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides: An Experimental–Computational Analysis of the Guest Inclusion Properties

The molecular recognition of nine quaternary alkyl- and aryl-ammonium halides (Bn) by two different receptors, Calkyl-tetrasodiumsulfonatomethyleneresorcinarene (An), were studied in solution using...

Selective Formation of S4- and T-Symmetric Supramolecular Tetrahedral Cages and Helicates in Polar Media Assembled via Cooperative Action of Coordination and Hydrogen Bonds

We report on the synthesis and self-assembly study of novel supramolecular monomers encompassing quadruple hydrogen-bonding motifs and metal-coordinating 2,2'-bipyridine units. When mixed with metal ions such as Fe2+ or Zn2+, the tetrahedron cage complexes are formed in quantitative yields and full diastereoselectivity, even in highly polar acetonitrile or methanol solvents. The symmetry of the complexes obtained has been shown to depend critically on the flexibility of the ligand. Restriction of the rotation of the hydrogen-bonding unit with respect to the metal-coordinating site results in a T-symmetric cage, whereas introducing flexibility either through a methylene linker or rotating be…

Synthesis of [5]Rotaxanes Containing Bi- and Tridentate Coordination Sites in the Axis

A new example of a linear [5]rotaxane has been synthesized by using the traditional "gathering-and-threading" approach but based on an unusual axle incorporating a symmetrical bis(bidentate) chelating fragment built on a 4,7-phenanthroline core. The stoppering reaction is particularly noteworthy since, instead of using a trivial bulky stopper as precursor to the blocking group, two semistoppered copper-complexed [2]pseudorotaxanes (namely [2]semirotaxanes) are used, which leads to the desired [5]rotaxane in good yield. The efficiency of the method relies on the use of "click" chemistry, with its very mild conditions, and on the protection by a transition-metal (copper(I)) of the various coo…

Tetraiodoethynyl resorcinarene cavitands as multivalent halogen bond donors

The first examples of iodoethynyl resorcinarene cavitands as rigid 3D halogen bond (XB) donor molecules are presented. These concave macrocycles form strong, RXB = 0.78–0.83, halogen bonds with dioxane oxygen, pyridine nitrogen and a bromide anion in tetraproropyl ammonium bromide resulting in deep cavity cavitand structures.

Solution and solid-state studies on the halide binding affinity of perfluorophenyl-armed uranyl–salophen receptors enhanced by anion–π Interactions

The enhancement of the binding between halide anions and a Lewis acidic uranyl-salophen receptor has been achieved by the introduction of pendant electron- deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion-p interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding.

Calix[4]arene-functionalized naphthalene and perylene imide dyes.

[reaction: see text] Calix[4]arenes bearing one, two, or four 1,8-naphthyl imide groups at the wide rim and bis-calix[4]arenes connected via perylene-bisimide dye spacers have been synthesized. The low-temperature NMR spectrum of the tetranaphthylimide suggests, in agreement with a crystal structure, a C2-symmetrical pinched cone conformation stabilized via face-to-face pi-pi interactions between opposite naphthylimide groups. UV-vis and fluorescence studies have been carried out for the perylene bis-calix[4]arene dyes.

Recognition of N-Alkyl- and N-Aryl-Acetamides by N-Alkyl Ammonium Resorcinarene Chlorides

N-alkyl ammonium resorcinarene chlorides are stabilized by an intricate array of intra- and intermolecular hydrogen bonds that leads to cavitand-like structures. Depending on the upper-rim substituents, self-inclusion was observed in solution and in the solid state. The self-inclusion can be disrupted at higher temperatures, whereas in the presence of small guests the self-included dimers spontaneously reorganize to 1:1 host-guest complexes. These host compounds show an interesting ability to bind a series of N-alkyl acetamide guests through intermolecular hydrogen bonds involving the carbonyl oxygen (C=O) atoms and the amide (NH) groups of the guests, the chloride anions (Cl(-)) and ammoni…

Reversible dehydration polymerization of terephthalate bridged [{Cu2(2,2′-bpy)2(tp)(H2O)3(NO3)}·H2O·NO3]2

The title compound is the first example of a molecular magnet sponge, which exhibits a carboxylate-assisted unique reversible dehydrative polymerization–rehydrative monomerization phenomenon.

Synthesis, reactions and structural features of monofluorinated cyclopropanecarboxylates

Abstract Monofluorinated cyclopropanecarboxylates are available in racemic or optically active form by transition metal-catalyzed reactions of vinylfluorides with diazoacetates. From α-fluorostyrene and tert-butyl diazoacetate in the presence of 2 mol% of an enantiopure bis(oxazoline) copper complex, a 81:19 mixture of tert-butyl trans- and cis-2-fluoro-2-phenylcyclopropanecarboxylates was obtained with high enantiomeric excess (ee) of 93 or 89%, respectively. The corresponding racemic ethylesters were used as starting materials for the synthesis of carboxamides, of the cis- and trans-isomers of analogues of tranylcypromine, an anti-depressive drug and several of its homologous fluorinated …

N-Heterocyclic carbenes from ylides of indolyl-imidazolium, azaindolyl-imidazolium, and indolyl-triazolium salts, and their borane adducts

Abstract Indol-2-yl-imidazolium salts were deprotonated at N1 of the indole ring to give ylides. Their tautomeric N-heterocyclic carbenes (NHCs) were trapped by sulfur to give imidazole-2-thiones. Treatment of the ylides with triethylborane resulted in the formation of zwitterionic borane adducts. An analogous sequence of reactions was performed with 8-azaindol-2-yl-imidazolium salts, which served as precursor to prepare first representatives of a new heterocyclic ring system on reaction of their NHC-tautomers with triethylborane. Similarly, an indol-2-yl-1,2,4-triazolium salt was examined with respect to ylide–NHC tautomerism and trapping reactions. A nucleophilic ring transformation of in…

Rare Crystal Structure of Open Spirolactam Ring along with the Closed-Ring Form of a Rhodamine Derivative : Sensing of Cu2+ Ions from Spinach

Crystal structures of a rhodamine derivative in its closed and open spirolactam ring forms were developed, which allows selective and sensitive detection of Cu2+ ions at a micromolar range in neutral medium. The chemosensing properties of the probe through a pentacoordinate Cu2+ ions were proven by spectroscopic and theoretical analysis. The spirolactam ring opening as the Cu2+selective sensor was applied to spinach (Spinacia oleracea) to estimate the accumulation of copper as copper(II) in the plant. peerReviewed

An electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric study of the gas-phase stabilities and fragmentation ofN-alkylammonium resorcarenes

Five N-alkylated ammonium resorcarene derivatives, differing either in the nitrogen atom or in the lower rim alkyl chain, were studied using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The main purpose was to clarify the fragmentation and the relative stabilities of the protonated molecules by collision-induced dissociation (CID) experiments. The results indicate that fragmentation of the upper rim alkyl amino substituents at the 2-position occurs readily. Variation in the gas-phase stabilities of these molecules was also observed. In addition, the proposed fragmentation pathways are depicted.

Incorporation of the bacterial reaction centre into dendrimersomes

For the first time the ability of the first generation dendrimer belonging to the family of polyester-benzylether, (3,5)12G1-PE-BMPA-(OH)4, to form dendrimersomes is presented together with their capability to reconstitute the integral membrane protein complex called Reaction Centre (RC) purified from the photosynthetic bacterium Rhodobacter sphaeroides. Size, polydispersity and time stability of the empty and protein containing dendrimersomes are presented together with the photochemical activity of the guest protein. The RC presence appears to strongly enhance the self-assembly properties of the Janus dendrimer, leading to the formation of proteo-dendrimersomes showing a photochemical act…

2,2′:6′,2″-Terpyridine Trimethylplatinum(IV) Iodide Complexes as Bifunctional Halogen Bond Acceptors

Three new organometallic trimethylplatinum(IV) iodide complexes of 2,2′:6′,2″-terpyridines have been synthesized and characterized by 1H NMR spectroscopy, mass spectrometry, elemental analysis, and single crystal X-ray diffraction analysis. The X-ray crystal structures of PtMe3I(L) complexes 1–3 {L for 1 = 4′-chloro-2,2′:6′,2″-terpyridine, 2 = 4′-(4-cyanophenyl)-2,2′:6′,2″-terpyridine, and 3 = 4′-(4-tolyl)-2,2′:6′,2″-terpyridine} reveal distorted octahedral coordination geometry of the platinum(IV) metal centers with bidentate coordination of the terpyridine ligands. Complexation of 1–3 with iodopentafluorobenzene (IPFB) afforded single-crystal structures of halogen bond (XB) complexes 1a–3…

Selective derivatisation of resorcarenes: 1. The regioselective formation of tetra-benzoxazine derivatives

Abstract Four 5,6-benzo-1,3-oxazine rings are formed by the condensation of resorcarenes with various aliphatic or aromatic primary amines and formaldehyde. From four possible regioisomers only the C4 symmetrical compound is isolated in yields of up to 90%. Semiempirical calculations confirm its relative stability, which is due to the possible formation of four intramolecular OH…O hydrogen bonds. The regioselectivity of the reaction is further established for two examples by single crystal X-ray analysis. A solvent molecule is included in the extended cavity.

Pentafluorophenyl salicylamine receptors in anion–π interaction studies

A crystal structure analysis confirms the appropriateness of pentafluorophenyl salicylamine (1a) as a π-acceptor for anion–π interactions. Crystals of 1a·HCl show that the OH-group fixes the anion in a η2-type binding motif above the electron-deficient arene. Attempts to find some relevance for this weak intermolecular force in solution failed. Stronger CH–, NH– and OH–anion interactions are dominant over the weak anion–π interactions. Due to the hydrogen bonding, the non-fluorinated receptor exhibits the highest binding constants within this series.

Asymmetric [N–I–N]+halonium complexes in solution?

Assessment of the solution equilibria of [bis(pyridine)iodine(I)]+ complexes by ESI-MS and NMR reveals the preference of iodine(I) to form complexes with a more basic pyridine. Mixtures of symmetric [bis(pyridine)iodine(I)]+ complexes undergo statistical ligand exchange, with a predominant entropic driving force favoring asymmetric systems. The influence of ligand basicity, concentration, temperature, and ligand composition is evaluated. Our findings are expected to facilitate the investigations, and the supramolecular and synthetic applications of halonium ions’ halogen bonds. peerReviewed

Evidence of the Facile Hydride and Enolate Addition to the Imine Bond of an Aluminum−Salophen Complex

The isolation of complexes 2 and 3, unambiguously characterized by single-crystal X-ray diffraction, demonstrates that nucleophilic additions to the aluminum-coordinated imino bond of salophen complex 1 can be achieved under very mild conditions.

Iron(III) chloride as mild catalyst for the dearomatizing cyclization of N-acylindoles

A catalytic approach for the preparation of indolines by dearomatizing cyclization is presented. FeCl3 acts as a catalyst to afford tetracyclic 5a,6-dihydro-12H-indolo[2,1-b][1,3]benzoxazin-12-ones in good yields. The cyclization also proceeds with tosylamides forming C-N bonds in 53 % yield. peerReviewed

Cover Picture: Achieving Strong Positive Cooperativity through Activating Weak Non‐Covalent Interactions (Angew. Chem. Int. Ed. 3/2018)

Selective recognition of aromatic hydrocarbons by endo-functionalized molecular tubes via C/N-H⋅⋅⋅π interactions

Abstract Molecular recognition of aromatic hydrocarbons by four endo -functionalized molecular tubes has been studied by 1 H NMR spectroscopy, computational methods, and single crystal X-ray crystallography. The binding selectivity is rationalized by invoking shape complementarity and dipole alignment. The non-covalent interactions are proved to predominantly be C/N-H⋅⋅⋅ π interactions.

CaCl2, Bisoxazoline, and Malonate: A Protocol for an Asymmetric Michael Reaction

A mild protocol for the asymmetric Michael addition of dimethyl malonate to various α,β-unsaturated carbonyl compounds was developed. The salient feature of this methodology is that a cheap and environmentally friendly Lewis acid, CaCl2, was used as a catalyst. An aminoindanol- and pyridine-derived ligand provided in the presence of CaCl2 Michael adducts in moderate to high enantioselectivities. The scope of the reaction was demonstrated.

Resorcarenes in the Boat Conformation as Building Blocks for Hydrogen-Bonded Assemblies Including Two Ammonium Cations

Crystal structures are reported for various co-crystals of rccc-resorcarenes with triethylammonium chloride. Usually, two molecules of a C2v-symmetric tetraester 2 in the boat conformation are linked through four hydrogen-bonded chloride anions to give dimeric assemblies. Two of the chloride anions may be replaced by four hydrogen-bonded ethanol molecules in an otherwise similar structure. These assemblies, which consist of six or eight components, posses voluminous, negatively charged chambers in which two triethylammionium cations, 3+, are included as guests by strong electrostatic and hydrogen-bonding interactions. The host-guest N-H...Cl hydrogen bonds were clearly detected at 173 K. Th…

Confinement inside a Crystalline Sponge Induces Pyrrole To Form N−H⋅⋅⋅π Bonded Tetramers

Based on the DFT‐level calculated molecular volume (V mol ) of pyrrole and its liquid density, pyrrole manifests the highest liquid density coefficient LD c (defined as [V mol • density • 0.6023]/FW) value of 0.7. Normal liquids have LD c < 0.63. This very high LD c is due to the strong N‐H … π interactions in solution and hence pyrrole can be considered to be a pseudo‐crystalline liquid. When trapped inside the confined space of the crystalline sponge a reorientation of the N‐H … π interaction is observed leading to specific cyclic N‐H … π tetramers and N‐H … π dimers, verified by single crystal X‐ray crystallographic and computational methods. These tetramers are of the same size as four …

Strong Emission Enhancement in pH-Responsive 2:2 Cucurbit[8]uril Complexes

Organic fluorophores, particularly stimuli-responsive molecules, are very interesting for biological and material sciences applications, but frequently limited by aggregation- and rotation-caused photoluminescence quenching. A series of easily accessible bipyridinium fluorophores, whose emission is quenched by a twisted intramolecular charge-transfer (TICT) mechanism, is reported. Encapsulation in a cucurbit[7]uril host gave a 1:1 complex exhibiting a moderate emission increase due to destabilization of the TICT state inside the apolar cucurbituril cavity. A much stronger fluorescence enhancement is observed in 2:2 complexes with the larger cucurbit[8]uril, which is caused by additional con…

ChemInform Abstract: Halogen-Bonded Supramolecular Complexes and Networks

In spite of some controversy of the true nature of the interaction between polarized halogen atoms and neutral or charged Lewis bases, termed “halogen bonding”, as a primary interaction, it is a very useful new tool/way to construct supramolecular complexes and networks. This is especially true in solid state supramolecular chemistry where utilization of weak intermolecular interactions such as halogen bonding opens up new insights to materials design and supramolecular synthesis.

Small hydrocarbon cyclophanes: Synthesis, X-ray analysis and molecular modelling

Small hydrocarbon cyclophanes, such as [2.2.0]m,m,m-cyclophane (20) and [2.2.0]p,m,m-cyclophane (21), are strained analogues of the well-known π-prismand [2.2.2]p,p,p-cyclophane (1). The synthetic route to these molecules is based on well-established cyclophane methodology which offers a general access to a whole family of hydrocarbon cyclophanes. Single crystal X-ray analysis and molecular modelling showed that the reduction of the ring size from 18-membered (1) to 14-membered (21) or 13-membered (20) has a substantial effect on the size and the shape of the cyclophane’s cavity, thus blocking its ability to complex Ag+ ions. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

5-Carbonyl-1,3-oxazine-2,4-diones from N-Cyanosulfoximines and Meldrum’s Acid Derivatives

At elevated temperatures, N-cyanosulfoximines react with Meldrum's acid derivatives to give sulfoximines with N-bound 5-carbonyl-1,3-oxazine-2,4-dione groups. A representative product was characterized by single-crystal X-ray structure analysis. The product formation involves an unexpected molecular reorientation requiring several sequential bond-forming and -cleaving processes.

Discriminating octahedral transition metal ions: highly selective tripodal tris-(2,2′-bipyridine) functionalized piperazine cyclophane receptor for Cu2+ ions

New tripodal transition metal ion receptors, tris(5-ethoxycarbonyl-2,2'-bipyridine) and tris(5-carboxylate-2,2'-bipyridine) substituted 27-membered trimeric piperazine cyclophanes 5 and 7 as well as tetra(5-ethoxycarbonyl-2,2'-bipyridine) substituted 36-membered tetrameric piperazine cyclophane 6, have been prepared and their transition metal ion complexing properties studied in solution by UV-vis spectroscopy and in the solid state by single-crystal X-ray diffraction. The crystal structures of [H(3)5(3+)·Fe(2+)]·4(ClO(4)(-))·CF(3)COO(-) (V), [H(3)7(2+)·Fe(2+)]·2(SO(4)(2-)) (VII) and the reference complex [tris(5,5'-bis(ethoxycarbonyl)-2,2'-bipyridine)Fe(II) perchlorate] (I) showed that the…

Diastereoselective Synthesis of Spiro[pyrazolone-4,3′-tetrahydrothiophenes] via a Sulfa-Michael/Aldol Domino Reaction

Synthesis : journal of synthetic organic chemistry 48(23), 4091-4098(2016). doi:10.1055/s-0035-1562473

Anion binding to resorcinarene-based cavitands: the importance of C-H...anion interactions.

An unusual magnetic response in a π-stacked 66-dia net structure of [4 + 2] copper(II) cubane

A phenoxo bridged antiferromagnetic copper(II) cubane, features a π-stacked 66 -dia net framework, which creates long range ferromagnetic ordering, as evidenced from a coercivity maximum (~2000 Oe) at 20K with very unusual saturation magnetization. peerReviewed

Unique copper ion catalyzed hydrolytic cleavage of C–N(2) bond of thiosemicarbazide

Abstract For the first time, stable but coordinatively unsaturated Cu(II) complexes [Cu(2,2′-bpy)X2] · xH2O (X = ClO4, NO3, CH3COO and 2,2′-bpy = 2,2′-bipyridyl) have been found to promote the hydrolysis of C–N(2) bond of thiosemicarbazide (tsc) at 25 °C and at neutral pH yielding monomeric [Cu(2,2′-bpy)(NCS)2]. Direct reaction between [Cu(2,2′-bpy)2]Cl2 · 6H2O, KSCN and CuCl2 results in polymeric [Cu(2,2′-bpy)(NCS)2]n [1] [Inorg. Chim. Acta. 286 (1999) 108]. Similarly tsc is cleaved by Cu(I) complex [Cu(ϕ3P)2(CH3CN)2]ClO4 [ϕ3P = triphenylphosphine] which itself is converted into dimeric [Cu(ϕ3P)2(NCS)]2.

Stacking of Sterically Congested Trifluoromethylated Aromatics in their Crystals – The Role of Weak F···π or F···F Contacts

European journal of organic chemistry : EurJOC 2020(38), 6073-6077 (2020). doi:10.1002/ejoc.202001008

Mixed valence mono- and hetero-metallic grid catenanes

Multicomponent self-assembly was employed to obtain, in the solid state, a series of mixed valence mono- and hetero-metallic grid catenanes, which were characterized by single crystal X-ray diffraction.

N-Alkyl Ammonium Resorcinarene Salts as High-Affinity Tetravalent Chloride Receptors.

N-Alkyl ammonium resorcinarene salts (NARYs, Y=triflate, picrate, nitrate, trifluoroacetates and NARBr) as tetravalent receptors, are shown to have a strong affinity for chlorides. The high affinity for chlorides was confirmed from a multitude of exchange experiments in solution (NMR and UV/Vis), gas phase (mass spectrometry), and solid-state (X-ray crystallography). A new tetra-iodide resorcinarene salt (NARI) was isolated and fully characterized from exchange experiments in the solid-state. Competition experiments with a known monovalent bis-urea receptor (5) with strong affinity for chloride, reveals these receptors to have a much higher affinity for the first two chlorides, a similar af…

Stereoselective Synthesis of Spiro-Decalin Oxindole Derivatives via Sequential Organocatalytic Michael-Domino Michael/Aldol Reaction.

A highly stereoselective procedure for the synthesis of spiro-polycyclic oxindoles bearing five contiguous stereogenic centers including two tetrasubstituted carbons has been developed. Under sequential organocatalysis performed by a pyrrolidine-based organocatalyst and DBU, a highly atom-economical Michael–domino Michael/aldol reaction sequence was optimized, yielding variously functionalized spiro-decalin oxindoles with excellent stereoselectivity (>99:1 dr, up to 92% ee). peerReviewed

Synthesis, characterization and thermal properties of small R2R′2N+X−-type quaternary ammonium halides

Twenty-one R {sub 2} R {sup '} {sub 2}N{sup +} X {sup -} -type (R=methyl or ethyl, R {sup '}=alkyl, X=Br or I) quaternary ammonium (QA) halides have been prepared by using a novel one-pot synthetic route in which a formamide (dimethyl-, diethylformamide, etc.) is treated with alkyl halide in the presence of sodium or potassium carbonate. The formation of QA halides was verified with {sup 1}H-NMR, {sup 13}C-NMR, MS and elemental analysis. The crystal structures of four QA halides (two bromide and two iodide) were determined using X-ray single crystal diffraction, and the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bu…

Effiziente Umwandlung von Licht in chemische Energie: Gerichtete, chirale Photoschalter mit sehr hohen Quantenausbeuten

Crystal Structures and Thermal Behavior of Bis(dibenzyldimethylammonium) Tetrabromometallates(II) [M = Mn(II), Co(II) and Zn(II)] and Their Solvates

Six new A2MBr4 structures [A = dibenzyldimethylammonium cation,M = Mn(II), Co(II) or Zn(II)] were crystallized with or without solvent molecules from acetonitrile, methanol and/or aqueous solutions. The isomorphous compounds [(Bz2Me2N)2][MnBr4]·CH3CN·H2O (1) and [(Bz2Me2N)2]-[ZnBr4]·CH3CN·H2O (4) crystallize in the triclinic space group P1̄ from acetonitrile solutions. The solvent molecules participate in the hydrogen bonding network inside the crystal structure. [(Bz2Me2N)2][CoBr4]·0.5CH3CN (2) crystallizes from an acetonitrile solution in the monoclinic space group P21/c. The solvent molecules fill the voids of the crystal structure. Compound 2 is isostructural with the previously reporte…

Iodine Clathrated: A Solid‐State Analogue of the Iodine–Starch Complex

Co-crystallizing iodine with a simple dicationic salt (1,8-diammoniumoctane chloride) results in the clathration of the iodine (I2 ) molecules inside trigonal and hexagonal helical channels of the crystal lattice with 72 wt % overall I2 loading. The I2 inside the bigger trigonal channel forms a I-I⋅⋅⋅I-I⋅⋅⋅I-I halogen-bonded infinite helical chain, while the I2 in the smaller hexagonal channel is disordered. In both channels the I2 interaction with the channel wall happens through I-I⋅⋅⋅Cl- halogen bonds. The helical channels in the crystal lattice are constructed via the strong charge-assisted H2 N+ H⋅⋅⋅Cl- hydrogen bonds between the dications and the chloride anions. The structure shows a…

Pienestä syntyi suurta = Nano came to Jyväskylä

Iodine Clathrated : A Solid-State Analog of the Iodine-Starch Complex

Co-crystallizing iodine with a simple dicationic salt (1,8- diammoniumoctane chloride) results in the clathration of the iodine (I2) molecules inside trigonal and hexagonal helical channels of the crystal lattice with 72 wt% overall I2 loading. The I2 inside the bigger trigonal channel forms a I-I•••I-I•••I-I halogen-bonded infinite helical chain, while the I2 in the smaller hexagonal channel is disordered. In both channels the I2 interaction with the channel wall happens through I-I•••Cl- halogen bonds. The helical channels in the crystal lattice are constructed via the strong charge-assisted H2N+ -H•••Cl- hydrogen bonds between the dications and the chloride anions. The structure shows a …

Melamine induced conformational change of ethyl resorcinarene in solid state

When ethyl resorcinarene (1) and melamine (2) are co-crystallised, all intramolecular hydrogen bonds keeping the resorcinarene in crown conformation are broken causing an unexpected conformational change to boat, and a highly ordered hydrogen bonded network is formed.

Crystal structures and absolute configurations of dexmedetomidine and its tosyl derivative

Abstract X-ray diffraction data were used to determine the absolute configuration of dexmedetomidine, a new member of a class of drugs with 4-arylalkyl-1H-imidazole structure. When the anomalous effect of the parent compound proved to be too small for determination of the absolute configuration the tosyl derivative, with the same configuration, was synthesised and used as a reference. Stability of the stereogenic center was verified by HPLC technique. The absolute configuration of the compounds is S. Complete crystal structures are reported for both compounds. Co radiation was used for measurements.

Asymmetric Synthesis of Five-Membered Spiropyrazolones via N-Heterocyclic Carbene (NHC)-Catalyzed [3+2] Annulations

A new synthetic strategy for the asymmetric synthesis of five-membered spiropyrazolones via N-heterocyclic carbene-catalyzed [3+2] annulations employing enals and unsaturated pyrazolones as substrates has been developed. The new protocol allows the flexible variation of all four substituents of the pharmaceutically important spiropyrazolones in moderate to very good yields and in most cases with excellent diastereoselectivities and good to excellent enantioselectivities.

Modified ent-Abietane Diterpenoids from the Leaves of Suregada zanzibariensis

The leaf extract of Suregada zanzibariensis gave two new modified ent-abietane diterpenoids, zanzibariolides A (1) and B (2), and two known triterpenoids, simiarenol (3) and β-amyrin (4). The structures of the isolated compounds were elucidated based on NMR and MS data analysis. Single-crystal X-ray diffraction was used to establish the absolute configurations of compounds 1 and 2. The crude leaf extract inhibited the infectivity of herpes simplex virus 2 (HSV-2, IC50 11.5 μg/mL) and showed toxicity on African green monkey kidney (GMK AH1) cells at CC50 52 μg/mL. The isolated compounds 1–3 showed no anti-HSV-2 activity and exhibited insignificant toxicity against GMK AH1 cells at ≥100 μM. p…

Piperazine bridged resorcinarene cages.

The one-pot Mannich condensation of resorcinarenes with piperazine and an excess of formaldehyde under high dilution conditions results in a helical cage, namely, a covalently linked dimer of two resorcinarenes connected via four piperazine bridges in yields ranging from 20 to 40%. The compounds were analyzed by NMR spectroscopy, ESI mass spectrometry, and single crystal X-ray diffraction. The helical cages can encapsulate small guest molecules by adapting the cavity volume by changing the helical pitch according to the guest size.

Weak Intermolecular Anion–π Interactions in Pentafluorobenzyl-Substituted Ammonium Betaines

A series of ammonium–carboxylate and ammonium–sulfonate betaines was synthesized and studied by single-crystal X-ray diffraction analysis to investigate the weak intermolecular interactions as well as the intramolecular interactions in the solid state. None of the expected intramolecular anion–π interactions could be observed, probably because of the steric demands and the reduced nucleophilicity of the anionic part of the betaines. Nevertheless, a weak intermolecular anion–π interaction between the anionic part of the betaine and the pentafluorophenyl unit is present in the structure of 5a.

Helicate Extension as a Route to Molecular Wires

We describe the preparation of a helicate containing four closely spaced, linearly arrayed copper(I) ions. This product may be prepared either directly by mixing copper(I) with a set of precursor amine and aldehyde subcomponents, or indirectly through the dimerization of a dicopper(I) helicate upon addition of 1,2-phenylenediamine. A notable feature of this helicate is that its length is not limited by the lengths of its precursor subcomponents: each of the two ligands wrapped around the four copper(I) centers contains one diamine, two dialdehyde, and two monoamine residues. This work thus paves the way for the preparation of longer oligo- and polymeric structures. DFT calculations and elec…

Alkoxy-, Acyloxy-, and Bromomethylation of Resorcinarenes

Reaction of resorcinarene octols with tris-hydroxymethylmethylamine (TRIS), formaldehyde, and alcohols results in tetraalkoxymethylation of the resorcinol rings. Harsh acylation of aminomethylated resorcinarenes with acid anhydrides leads to the complete acylation of eight hydroxyls and substitution of the amino versus acyloxy groups. Acyloxymethylated resorcinarene 6b can be transformed into a tetrabromomethylated derivative 7 through the reaction with HBr in acetic acid.

Amidino substituted 2-aminophenols: biologically important building blocks for the amidino-functionalization of 2-substituted benzoxazoles

Unlike the closely related and widely investigated amidino-substituted benzimidazoles and benzothiazoles with a range of demonstrated biological activities, the matching benzoxazole analogues still remain a largely understudied and not systematically evaluated class of compounds. To address this challenge, we utilized the Pinner reaction to convert isomeric cyano-substituted 2- aminophenols into their amidine derivatives, which were isolated as hydrochlorides and/or zwitterions, and whose structure was confirmed by single crystal X-ray diffraction. The key step during the Pinner synthesis of the crucial carboximidate intermediates was characterized through mechanistic DFT calculations, with…

Substituent Effects on the [N-I-N](+) Halogen Bond

We have investigated the influence of electron density on the three-center [N-I-N](+) halogen bond. A series of [bis(pyri din e) io dine](+) and [1,2-bis ( (pyridin e-2-71 ethynyl)b e nze n e)io dine](+) BF4- complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by N-15 NMR and by computation of the natural atomic population and the pi electron population of the nitrogen atoms. Formation of the [N-…

Synthesis of tetrahalide dianions directed by crystal engineering

CrystEngComm 17(35), 6641-6645(2015). doi:10.1039/C5CE01288K

Anion-Exchange Properties of Trifluoroacetate and Triflate Salts of N-Alkylammonium Resorcinarenes

The synthesis of N-benzyl- and N-cyclohexylammonium resorcinarene trifluoroacetate (TFA) and triflate (OTf) salt receptors was investigated. Solid-state analysis by single-crystal X-ray diffraction revealed that the N-alkylammonium resorcinarene salts (NARSs) with different upper substituents had different cavity sizes and different affinities for anions. Anion-exchange experiments by mixing equimolar amounts of N-benzylammonium resorcinarene trifluoroacetate and N-cyclohexylammonium resorcinarene triflate, as well as N-benzylammonium resorcinarene triflate and N-cyclohexylammonium resorcinarene trifluoroacetate showed that the NARS with flexible benzyl groups preferred the larger OTf anion…

Aromatic Bridged Bis-phenol A Derived Cyclophanes. Synthesis, Molecular Structure and Binding Properties Toward Quats

Three novel polyoxyethylene bridged bis phenol A derived cyclophanes, {\rm 2 -- 4,} with additional aromatic units in the bridge to increase the number of cation–π interactions with guest cations, were synthesized and characterized by means of X-ray crystal structure determinations. The binding properties of these receptors toward tetramethylammonium (TMA), N-methylpyridinium (NMP), acetylcholine (ACh) and N-methylquinolinium (NMQ) salts were evaluated by means of 1H NMR spectroscopy and compared with those of the previously reported receptor 1.

Coordination-Induced Spin-State Switching with Nickel Chlorin and Nickel Isobacteriochlorin

We present the first coordination-induced spin-state switching with nickel chlorin and nickel isobacteriochlorin. The spin-state switching was monitored by UV-vis spectroscopy and NMR titration experiments. The association constants (K1 and K2) and thermodynamic parameters (ΔH and ΔS) of the coordination of pyridine were determined. The first X-ray analyses of a paramagnetic nickel chlorin and a nickel isobacteriochlorin provide further information about the structure of the octahedral complexes. Nickel chlorin and even more pronounced nickel isobacteriochlorin exhibit stronger coordination of axial ligands compared to the corresponding nickel porphyrin and thus provide the basis for more e…

Role of Weak Hydrogen Bonds and Halogen Bonds in 5-Halo-1,3-dimethyluracils and Their Cocrystals : A Combined Experimental and Computational Study

Seven single crystals containing either N,N-dimethyluracil (DMHU) or one of its 5-halogenated derivatives (DMXU; X = F, Cl, Br, I) were prepared using N,N-dimethylformamide as the crystallization solvent. Single crystal X-ray diffraction and quantum chemical calculations carried out at the spin component scaled local MP2 level of theory were then used to study the intramolecular halogen and nonconventional hydrogen bonds present in the structures. The results were compared to and contrasted with the previously reported data for uracil and its halogenated derivatives. In particular, the intermolecular interactions in DMIU were compared to the halogen and hydrogen bonds in 5-iodouracil that, …

Frontispiece: An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior

Neue extrem deformierte (Biphenylen‐)Kohlenwasserstoff‐Gerüste

New Extremely Deformed (Biphenylene)Hydrocarbon Skeletons The tetracyclic carbon skeleton 2-oxo[3](1,8)biphenylenophane (4) was synthesized by cyclization of a mixture of the bis(bromomethyl) compounds 7a, b with p-tolylsulfonylmethyl isocyanide. 2-Hydroxy[3](1,8)biphenylenophane (5) and the [3](1,8)biphenylenophane hydrocarbon 6 were obtained by reduction of 4 with LiAlH4 and NaBH4, respectively. X-ray analyses of 4 and 6 illustrate the dramatic deformation of bond lengths and angles in these molecules.

(E)-7-(Pyren-1-yl)hept-6-enoic acid

The title compound, C23H20O2, is a precursor of a pyrene-based supramolecular element for non-covalent attachment to a carbon nanotube. The asymmetric unit contains three independent molecules. The carboxylic acid group in each of these molecules serves as an intermolecular hydrogen-bond donor and acceptor, generating the commonly observed double O&amp;#8212;H...O hydrogen-bond motif in an eight-membered ring. Weaker C&amp;#8212;H...O, &amp;#960;&amp;#8211;&amp;#960; [centroid&amp;#8211;centroid distance = 3.968&amp;#8197;(4)&amp;#8197;&amp;#197;] and C&amp;#8212;H...&amp;#960; interactions are also found in the crystal structure.

Heterometallic Au(I)–Cu(I) Clusters : Luminescence Studies and 1O2 Production

Two different organometallic gold(I) compounds containing naphthalene and phenanthrene as fluorophores and 2-pyridyldiphenylphosphane as the ancillary ligand were synthesized (compounds 1 with naphthalene and 2 with phenanthrene). They were reacted with three different copper(I) salts with different counterions (PF6–, OTf–, and BF4–; OTf = triflate) to obtain six Au(I)/Cu(I) heterometallic clusters (compounds 1a–c for naphthalene derivatives and 2a–c for phenanthrene derivatives). The heterometallic compounds present red pure room-temperature phosphorescence in both solution, the solid state, and air-equilibrated samples, as a difference with the dual emission recorded for the gold(I) precu…

Polyoxygenated Cyclohexenes and Other Constituents of Cleistochlamys kirkii Leaves.

Thirteen new metabolites, including the polyoxygenated cyclohexene derivatives cleistodiendiol (1), cleistodienol B (3), cleistenechlorohydrins A (4) and B (5), cleistenediols A-F (6-11), cleistenonal (12), and the butenolide cleistanolate (13), 2,5-dihydroxybenzyl benzoate (cleistophenolide, 14), and eight known compounds (2, 15-21) were isolated from a MeOH extract of the leaves of Cleistochlamys kirkii. The purified metabolites were identified by NMR spectroscopic and mass spectrometric analyses, whereas the absolute configurations of compounds 1, 17, and 19 were established by single-crystal X-ray diffraction. The configuration of the exocyclic double bond of compound 2 was revised base…

A conformationally adaptive macrocycle : conformational complexity and host–guest chemistry of zorb[4]arene

Large amplitude conformational change is one of the features of biomolecular recognition and is also the basis for allosteric effects and signal transduction in functional biological systems. However, synthetic receptors with controllable conformational changes are rare. In this article, we present a thorough study on the host–guest chemistry of a conformationally adaptive macrocycle, namely per-O-ethoxyzorb[4]arene (ZB4). Similar to per-O-ethoxyoxatub[4]arene, ZB4 is capable of accommodating a wide range of organic cations. However, ZB4 does not show large amplitude conformational responses to the electronic substituents on the guests. Instead of a linear free-energy relationship, ZB4 foll…

Halogen-Bonded [N–I–N]− Complexes with Symmetric or Asymmetric Three-Center–Four-Electron Bonds

A series of LH[Z–I–Z] halogen(I) complexes, where Z = saccharinato or phthalimido anions and LH = pyridinium, pyrazinium, tetrabutyl (TBA)- or tetramethylammonium (TMA) cations, were prepared, structurally characterized, and discussed as complexes consisting of a [N–I–N]− anion with a three-center–four-electron (3c-4e) halogen bond, and a hydrogen-bonding (pyridinium or pyrazinium) or inert (TBA or TMA) cation. The symmetric [N–I–N]− anion, reminiscent of the triiodide [I–I–I]− anion, is found to be structurally equivalent to its cationic analogue [N–I–N]+ with N–I bond lengths of 2.26 Å. In contrast to the homoleptic [N–I–N]+ complexes, asymmetry of the N–I bond lengths (2.21 and 2.28 Å) w…

Thiourea-Catalyzed Domino Michael–Mannich [3+2] Cycloadditions: A Strategy for the Asymmetric Synthesis of 3,3′-Pyrrolidinyl-dispirooxindoles

The asymmetric synthesis of trifluoromethylated 3,3′-pyrrolidinyl-dispirooxindole derivatives with four contiguous stereogenic centers, including two vicinal spiro-stereocenters, is described. Employing a bifunctional thiourea catalyst, a domino Michael–Mannich [3+2] cycloaddition occurs readily between isatin ketimines and isatin-derived enoates with good yields and very high stereoselectivities, providing a direct entry to the title compounds of potential medical value.

Very Large Container Molecules

N-Alkyl ammonium resorcinarene salts: multivalent halogen-bonded deep-cavity cavitands

N-Cyclohexyl ammonium resorcinarene halides, stabilized by an intricate array of hydrogen bonds in a cavitand-like assembly, form multivalent halogen-bonded deep-cavity cavitands with perfluoroiodobenzenes. As observed from the macromolar to infinite concentration range through crystal growth and single crystal X-ray analyses, four 1,4-diiodotetrafluorobenzenes form moderate halogen bonds with the bromides of the N-cyclohexyl ammonium resorcinarene bromides leading to a deep-cavity cavitand-like structure. In this assembly, the N-cyclohexyl ammonium resorcinarene bromide also acts as a guest and sits in the upper cavity of the assembly interacting with the 1,4-diiodotetrafluorobenzene throu…

Photocontrolled On-Surface Pseudorotaxane Formation with Well-Ordered Macrocycle Multilayers.

The photoinduced pseudorotaxane formation between a photoresponsive axle and a tetralactam macrocycle was investigated in solution and on glass surfaces with immobilized multilayers of macrocycles. In the course of this reaction, a novel photoswitchable binding station with azobenzene as the photoswitchable unit and diketopiperazine as the binding station was synthesized and studied by NMR and UV/Vis spectroscopy. Glass surfaces have been functionalized with pyridine-terminated SAMs and subsequently with multilayers of macrocycles through layer-by-layer self assembly. A preferred orientation of the macrocycles could be confirmed by NEXAFS spectroscopy. The photocontrolled deposition of the …

Synthesis and structural characterization of new transition metal complexes of a highly luminescent amino-terpyridine ligand

The synthesis, NMR and UV-Vis spectroscopy measurements and X-ray diffraction analysis of four new metal complexes of the amino terpyridine ligand 4́-[4-(4-aminophenyl)phenyl]-2,2́:6́,2́́-terpyridine L, namely [FeL2](ClO4)2 (1), [ZnL2](ClO4)2 (2), [CdL2](ClO4)2 (3) and [PtMe3IL] (4), are reported. The X-ray crystal structures of complexes 1-3 are 1:2 metal:ligand structures with tridentate ligands decorated around the octahedral metal centers. In complex 4, with L in a bidentate coordination mode, the Pt(IV) coordinated methyl and iodine groups form a fac-arrangement. The 1H NMR spectrum of 4 shows three 195Pt-1H resonances for the methyl groups incorporating the fac-arrangement, which conf…

Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution

A novel eight-membered macrocycle of the hemicucurbit[n]uril family, chiral (all-R)-cyclohexanohemicucurbit[8]uril (cycHC[8]) binds anions in a purely protic solvent with remarkable selectivity. The cycHC[8] portals open and close to fully encapsulate anions in a 1 : 1 ratio, resembling a molecular Pac-Man™. Comprehensive gas, solution and solid phase studies prove that the binding is governed by the size, shape and charge distribution of the bound anion. Gas phase studies show an order of SbF6− ≈ PF6− > ReO4− > ClO4− > SCN− > BF4− > HSO4− > CF3SO3− for anion complexation strength. An extensive crystallographic study reveals the preferred orientations of the anions within the octahedral cav…

Pyrene derived functionalized low molecular weight organic gelators and gels

Pyrene derived binary functionalized low molecular weight organic gelators (FLMOGs) and gels thereof in selected organic solvents were synthesized and characterized. The functionality refers to a functional group that does not take part in formation of the supramolecular gel network, but remains free and available for other purposes, such as to bind nanoparticles or other molecules into the gel structure. Functional groups were observed to disturb gel formation strongly, if they interact with each other within the same supramolecule due to the formation of competitive structures. Preventing such interactions restored the original gel properties. A gel with weaker supramolecular bonding than…

Cooperatively Enhanced Ion Pair Binding with a Hybrid Receptor

A simple 18-crown-6-based bis-urea receptor R(1) was synthesized in three steps from a commercial starting material. The receptor's behavior toward anions, cations, and ion pairs was studied in solution with (1)H NMR, in solid state with single-crystal X-ray diffraction, and in gas phase with mass spectrometry. In 4:1 CDCl3/dimethyl sulfoxide solution the receptor's binding preference of halide anions is I(-) < Br(-) < Cl(-) following the trend of the hydrogen-bonding acceptor ability of the anions. The receptor shows a remarkable positive cooperativity toward halide anions Cl(-), Br(-), and I(-) when complexed with Na(+), K(+), or Rb(+). The solid-state binding modes of R(1) with alkali an…

Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency

The spin–spin interactions between unpaired electrons in organic (poly)radicals, especially nitroxides, are largely investigated and are of crucial importance for their applications in areas such as organic magnetism, molecular charge transfer, or multiple spin labeling in structural biology. Recently, 2,2,6,6-tetramethylpiperidinyloxyl and polymers functionalized with nitroxides have been described as successful redox mediators in several electrochemical applications; however, the study of spin–spin interaction effect in such an area is absent. This communication reports the preparation of a novel family of discrete polynitroxide molecules, with the same number of radical units but differe…

Definition of the chalcogen bond (IUPAC Recommendations 2019)

Abstract This recommendation proposes a definition for the term “chalcogen bond”; it is recommended the term is used to designate the specific subset of inter- and intramolecular interactions formed by chalcogen atoms wherein the Group 16 element is the electrophilic site.

Helicates with Ether-Substituted Catechol Esters as Ligands

European journal of organic chemistry 2020(32), 5161-5172 (2020). doi:10.1002/ejoc.202000843

Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

A series of alkynyl gold(I) tri and tetratopic metallaligands of the type [Au3(CuC-R)3(μ3-triphosphane)] (R = 2,2'-bipyridin-5-yl or C10H7N2, 2,2':6',2''-terpyridin-4-yl or C15H10N3; triphosphane = 1,1,1-tris(diphenylphosphanyl) ethane or triphos, 1,3,5-tris(diphenylphosphanyl)benzene or triphosph) and [Au4(CuC-R)4 (μ4-tetraphosphane)] (R = C10H7N2, C15H10N3; tetraphosphane = tetrakis(diphenylphosphanylmethyl)methane or tetraphos, 1,2,3,5-tetrakis(diphenylphosphanyl)benzene or tpbz, tetrakis(diphenylphosphaneylmethyl)-1,2- ethylenediamine or dppeda) were obtained in moderate to good yields. All complexes could be prepared by a Q4 reaction between the alkynyl gold(I) polymeric species [Au(Cu…

The Recognition of Viologen Derivatives in Water by N-Alkyl Ammonium Resorcinarene Chlorides

Three water-soluble N-alkyl ammonium resorcinarene chlorides decorated with terminal hydroxyl groups at the lower rims were synthesized and characterized. The receptors were decorated at the upper rim with either terminal hydroxyl, rigid cyclohexyl, or flexible benzyl groups. The binding affinities of these receptors toward three viologen derivatives, two of which possess an acetylmethyl group attached to one of the pyridine nitrogens, in water were investigated via 1H NMR spectroscopy, fluorescence spectroscopy, and isothermal titration calorimetry (ITC). ITC quantification of the binding process gave association constants of up to 103 M-1. Analyses reveal a spontaneous binding process whi…

Halogen bonds in 2,5-dihalopyridine-copper(II) chloride complexes

Ten coordination complexes obtained through a facile reaction between 2,5-dihalopyridines and copperIJII) chloride (CuCl2) are characterized using single crystal X-ray diffraction. Two series of dihalopyridine complexes based on 2-chloro-5-X-pyridine and 2-bromo-5-X-pyridine (X = F, Cl, Br and I) were prepared to analyze the C–X2/X5⋯Cl–Cu halogen bonds (XB). The influence of X2- and X5-substituents on the respective interactions was examined by comparing them to the X2/X3⋯Cl–Cu XBs found in mono-substituted halopyridine complexes, (n-X-pyridine)2·CuCl2 (n = 2, 3 and X = Cl, Br and I). Varying the X5-halogens in (2,5-dihalopyridine)2·CuCl2, the C5–X5⋯Cl–Cu XBs follow the order F5 1 and they c…

2H -[1,3]Oxazino[3,2-α]indolin-4(3H )-ones: A Class Of Polyheterocyclic Indole-Based Compounds

Protonation of a Spherical Macrotricyclic Tetramine: Water Inclusion, Allosteric Effect, and Cooperativity

The spherical macrotricyclic cryptand tetramine "C24" (1) displays remarkable protonation behaviour. It undergoes protonation in four successive steps for which pKa values of 11.17±0.05, 10.28±0.04, 6.00±0.06 and 3.08±0.08 have been determined at 298 K. The unusually close values for the first two protonations provide evidence for the encapsulation of a water molecule serving as effector for the second protonation, which is consistent with earlier observations that the exchange of protons bound in the diprotonated species with solvent protons is unusually slow and that 17 O NMR spectra show the presence of an oxygen centre in the same species quite distinct from that of solvent water. Encap…

Asymmetric synthesis of cyclopentanes bearing four contiguous stereocenters via an NHC-catalyzed Michael/Michael/esterification domino reaction.

An NHC-catalyzed Michael/Michael/esterification domino reaction via homoenolate/enolate intermediates for the asymmetric synthesis of tetrasubstituted cyclopentanes is described.

The Important Role of the Nuclearity, Rigidity, and Solubility of Phosphane Ligands in the Biological Activity of Gold(I) Complexes

A series of 4-ethynylaniline gold(I) complexes containing monophosphane (1,3,5-triaza-7-phosphaadamantane (pta; 2), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (3), and PR3 , with R=naphthyl (4), phenyl (5), and ethyl (6)) and diphosphane (bis(diphenylphosphino)acetylene (dppa; 7), trans-1,2-bis(diphenylphosphino)ethene (dppet; 8), 1,2-bis(diphenylphosphino)ethane (dppe; 9), and 1,3-bis(diphenylphosphino)propane (dppp; 10)) ligands have been synthesized and their efficiency against tumor cells evaluated. The cytotoxicity of complexes 2-10 was evaluated in human colorectal (HCT116) and ovarian (A2780) carcinoma as well as in normal human fibroblasts. All the complexes showed a hi…

Two (E)-2-({[4-(dialkylamino)phenyl]imino}methyl)-4-nitrophenols.

The slow evaporation of analytical NMR samples resulted in the formation of crystals of (E)-2-({[4-(dimethylamino)phenyl]imino}methyl)-4-nitrophenol, C15H15N3O3, (I), and (E)-2-({[4-(diethylamino)phenyl]imino}methyl)-4-nitrophenol, C17H19N3O3, (II). Despite the small structural difference between these twoN-salicylideneaniline derivatives, they show different space groups and diverse molecular packing. The molecules of both compounds are close to being planar due to an intramolecular O—H...N hydrogen bond. The 4-alkylamino-substituted benzene ring is inclined at an angle of 13.44 (19)° in (I) and 2.57 (8)° in (II) with respect to the 4-nitro-substituted phenol ring. Only very weak intermole…

A modular "toolbox" approach to flexible branched multimacrocyclic hosts as precursors for multiply interlocked architectures.

Tetralactam macrocycles can be functionalized by a variety of cross-coupling reactions. A modular “toolbox” strategy is presented that allows 1) several tetralactam macrocycles to be covalently connected with each other or with a central spacer, 2) the macrocycles to be substituted with or connected to different chromophores, and 3) metal-coordination sites to be attached to the macrocycles. With this approach a series of different oligo-macrocyclic hosts was obtained with great structural diversity and enormous potential for further functionalization. Rotaxanes made on the basis of these macrocycles have been synthesized to demonstrate their utility in building more complex supramolecular …

Control of N-Heterocyclic Carbene Catalyzed Reactions of Enals: Asymmetric Synthesis of Oxindole-γ-Amino Acid Derivatives.

A strategy to control the switch between a non‐cycloaddition reaction and a cycloaddition reaction of enals, using N‐heterocyclic carbene (NHC) catalyisis, has been developed. The new scalable protocol leads to γ‐amino‐acid esters bearing a tetrasubstituted stereocenter in good yields and high stereoselectivities by homo‐Mannich reactions of enals and isatin‐derived ketimines. By simply changing the N‐ketimine substituent to an ortho‐hydroxy phenyl group, the corresponding spirocyclic oxindolo‐γ‐lactams are obtained. peerReviewed

Multinuclear magnetic resonance and x-ray diffraction studies of aminonitropyridines

The 15N NMR spectra for 21 aminonitropyridines were measured and their chemical shifts assigned. The 1H and 13C NMR chemical shifts and spin–spin coupling constants were also determined for 16 compounds of this series. In order to relate the structural properties of nitramino groups and their 15N NMR chemical shifts in 2- and 4-nitramino-3-nitropyridines, which differ remarkably from all other amino groups studied, low-temperature 1H NMR, 17O NMR, comparative INEPT and IR spectroscopic studies were carried out. In addition, the x-ray crystal structure of 2-nitramino-3-nitropyridine was determined. Comparative spectroscopic studies showed that the nitramino derivatives exhibit different char…

ChemInform Abstract: N1-Functionalized Indole-Phosphane Oxazoline (IndPHOX) Ligands in Asymmetric Allylic Substitution Reactions.

N-Functionalized IndPHOX ligands bearing various groups have been synthesized and the effects of the N1-substituent on the reaction rate, yield, and asymmetric induction in a palladium-catalyzed allylic substitution reaction are reported. The presence of an oxygen atom in the ligands, namely an N-MOM or N-THP group, led to enhancement of the enantioselectivity in the allylic amination reaction. In addition, a ligand with a chiral oxazoline ring at C-1 and a phosphane substituent at C-2 provided high enantioselectivity in good yield in an asymmetric allylic alkylation reaction.

Zinc-salophen complexes as selective receptors for tertiary amines

Zinc-salophen compounds 1-3 incorporating in the given order 1,2-diaminobenzene, 2,3-diaminonaphthalene, and 9,10-diaminophenantrene moieties were synthesised. Their binding properties toward a series of tertiary amines were assessed by UV-Vis and fluorescence spectroscopy in chloroform solution. Unprecedented selectivities of quinuclidine vs. triethylamine higher than 105 were recorded, thereby revealing the dramatic influence of steric effects on axial coordination of tertiary amines. X-Ray diffraction analyses showed that in the solid state compound 2 is dimeric, but its 1 : 1 quinuclidine complex is monomeric. Strong indications were obtained that both free receptors and their amine add…

Titelbild: Achieving Strong Positive Cooperativity through Activating Weak Non‐Covalent Interactions (Angew. Chem. 3/2018)

Mechanochemical Synthesis, Photophysical Properties, and X-ray Structures of N-Heteroacenes

The described mechanochemical methodology is an example of a proof-of-concept in which solution-based tedious, poor yielding, and difficult syntheses of pyrazaacenes are achieved under solvent-free ball-milling conditions; the method is easy, high yielding, time-efficient, and environmentally benign. The synthesized compounds also include pyrazaacenes (N-heteroacenes) that are octacene analogues containing pyrene building blocks. The compounds were sparingly soluble in common solvents, and column chromatographic purifications could be avoided after the solvent-free syntheses. The UV/Vis absorption spectra of the pyrazaacenes show intense absorption bands in the near-IR region. The single-cr…

Self-organized nanostructures of poly(4-vinylpyridine), polyaniline and polyamides due to metal complexation

Comb-shaped supramolecules are constructed using flexible polymers and semi-rigid conjugated undoped or doped conjugated polymers upon complexing Zinc dodecyl benzene sulphonate, Zn(DBS) 2 . Self-organized nanostructures are formed in the bulk due to competing attractive interactions (coordination or water mediated hydrogen bonding) and repulsive polar/nonpolar interactions, showing characteristic long periods of ca. 30 A.

Pentameric Circular Iron(II) Double Helicates and a Molecular Pentafoil Knot

We report on the synthesis of 11 pentameric cyclic helicates formed by imine condensation of alkyl monoamines with a common bis(formylpyridine)bipyridyl-derived building block and iron(II) and chloride ions. The cyclic double-stranded helicates were characterized by NMR spectroscopy, mass spectrometry, and in the case of a 2,4-dimethoxybenzylamine-derived pentameric cyclic helicate, X-ray crystallography. The factors influencing the assembly process (reactant stoichiometry, concentration, solvent, nature and amount of anion) were studied in detail: the role of chloride in the assembly process appears not to be limited to that of a simple template, and larger circular helicates observed with…

Nucleophilic iodonium interactions (NIIs) in 2-coordinate iodine(i) and silver(i) complexes

The generality of nucleophilic iodonium interactions (NIIs) has been demonstrated by preparing a range of silver(i) and iodonium (I+) complexes and studying their 15N NMR chemical shifts, with the first example of a NII-complex involving a 2-coordinate silver(i) complex being confirmed by X-ray crystallography, and its nucleophilicity studied by DFT calculations.

Synthesis, characterization, crystal structures and magnetic exchange in dinuclear copper complexes with 3-amino-1-propanol as terminal and bridging ligand

Abstract The synthesis, X-ray structures and spectroscopic and magnetic properties are described for two groups of dinuclear Cu(II) compounds with the ligand 3-amino-1-propanol (Hap). The formulae of the compounds are for group A: [Cu(ap)(anion)]2, in which ap is the dehydronated Hap and the anions are formate, nitrate, chloride and bromide and for group B: [Cu(ap)(Hap)]2(anion)2, with anion = iodide, bromide, chloride, nitrate and tetrafluoroborate. The structure of group A compounds consists of dinuclear units with the co-planar centrosymmetric chromophore ANCuOO′CuNA, in which the A ligands (anions) bridge to neighbouring units as axial ligands, thereby forming infinite chains. Dimer Cu……

Electron-Deficient Pyridylimines: Versatile Building Blocks for Functional Metallosupramolecular Chemistry

Metallosupramolecular systems heavily rely on the correct choice of ligands to obtain materials with desired properties. Engaging this problem, we present three ligand systems and six of their mono- and dinuclear complexes, based on the subcomponent self-assembly approach using electron-deficient pyridylcarbaldehyde building blocks. The properties are examined in solution by NMR and UV-vis spectroscopy and CV measurements as well as in solid state by single crystal X-ray diffraction analysis. Ultimately, the choice of ligands allows for fine-tuning of the electronic properties of the metal centers, complex-to-complex transformations, as well as establishing distinct anion-π-interaction moti…

All-Solid-State Ag+-ISE Based on [2.2.2]p,p,p-Cyclophane

All-solid-state ion-selective electrodes (ISEs) based on two ionophores with similar structure, i.e., [2.2.2] p,p,p-cyclophane and [2.2.2]m,p,p-cyclophane, were prepared and investigated. The ion-selective membranes were composed of the corresponding ionophore (1 %), potassium tetrakis(4-chlorophenyl)borate (0.5 %), 2-nitrophenyl octyl ether (65–66 %), and PVC (33 %). The ion-selective membrane was placed on top of a layer of the conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), working as ion-to-electron transducer. The resulting all-solid-state ISEs were conditioned in 0.01 M AgNO3 and investigated as Ag+-ISEs. The results show that [2.2.2] p,p,p-cyclophane is much more select…

Crystal Engineering Studies of the Complexes of Ethyl Resorcinarene with Aromatic Nitrogen Heterocycles

Five X-ray structures of complexes of ethyl resorcinarene with aromatic nitrogen heterocycles (imidazole, 1,2,4-triazole, pyridine, pyrazine, 2-pyridylmethanol and quinoline) show that ethyl resorcinarene spontaneously forms molecular inclusion complexes with five- and six-membered aromatic nitrogen heterocycles via π π and CH π interactions. However, with 10-membered quinoline, no molecular inclusion complex is formed. Instead, quinoline manifests crystal lattice inclusion.

Cocrystal trimorphism as a consequence of the orthogonality of halogen- and hydrogen-bonds synthons.

True trimorphic cocrystals, i.e. multi-component molecular crystals of identical composition that exhibit three polymorphic structures, are exceedingly rare and so far no halogen-bonded cocrystal system has been reported to exhibit trimorphism. Here we describe a unique example of a trimorphic cocrystal exhibiting both hydrogen and halogen bonds in which the differences between polymorphs reveal their orthogonality, evident by the apparently independent variation of well-defined hydrogen- and halogen-bonded motifs. peerReviewed

Tetrameric and Dimeric [N∙∙∙I+∙∙∙N] Halogen-Bonded Supramolecular Cages

Tripodal N-donor ligands are used to form halogen-bonded assemblies via structurally analogous Ag+-complexes. Selective formation of discrete tetrameric I6L4 and dimeric I3L2 halonium cages, wherein multiple [N∙∙∙I+∙∙∙N] halogen bonds are used in concert, can be achieved by using sterically rigidified cationic tris(1-methyl-1-azonia-4-azabicyclo[2.2.2]octane)-mesitylene ligand, L1(PF6)3, and flexible ligand 1,3,5-tris(imidazole-1-ylmethyl)-2,4,6-trimethylbenzene, L2, respectively. The iodonium cages, I6L14(PF6)18 and I3L22(PF6)3, were obtained through the [N∙∙∙Ag+∙∙∙N] → [N∙∙∙I+∙∙∙N] cation exchange reaction between the corresponding Ag6L14(PF6)18 and Ag3L22(PF6)3 coordination cages, prepar…

A New Macrobicyclic Tris-bipyridine Ligand and Its Cu2I and Ag3I Complexes

Concerted Halogen-Bonded Networks with N-Alkyl Ammonium Resorcinarene Bromides: From Dimeric Dumbbell to Capsular Architectures

N-Alkyl ammonium resorcinarene bromides and 1,4-diiodooctafluorobutane via multiple intermolecular halogen bonds (XB) form different exotic supramolecular architectures through subtle changes of the upper rim substituents. Dimeric dumbbell-like assembly with encapsulated guest molecules is generated with N-benzyl substituents. The N-hexyl groups engender an XB-induced polymeric pseudocapsule and an XB-induced dimeric capsule with entrapped 1,4-dioxane guest molecules. The N-propyl and N-cyclohexyl groups generate deep cavity cavitands. The deep cavity cavitands possess cavities for self-inclusion leading to polymeric herringbone arrangement in one direction and that pack into 3D polymeric a…

endo-Functionalized molecular tubes : selective encapsulation of neutral molecules in non-polar media

Four endo-functionalized molecular tubes with urea/thiourea groups in the deep cavities have been synthesized, and their binding ability to neutral molecules studied. Very high binding affinity and selectivity have been achieved, which are rationalized by invoking the shape and electrostatic complementarity and dipole alignment.

In the Pursuit of Efficient Anion-Binding Organic Ligands Based on Halogen Bonding

The syntheses and the crystal structures of new multitopic anion-binding organic ligands based on a benzenoid scaffold and bearing two or three 2-iodo-imidazolium arms are reported. The quite short...

Synthesis and thermal behavior of Janus dendrimers, part 2

Abstract The thermal properties of twelve Janus-type dendrimers up to the second generation were evaluated by termogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Compounds consist of the dendritic bisMPA based polyester moieties, and either 3,4-bis-dodecyloxybenzoic acid, 3,5-bis-dodecyloxybenzoic acid or 3,4,5-tris-dodecyloxybenzoic acid moieties, attached to opposite sides of the pentaerythritol core. The thermal stability of the compounds was evaluated by TGA, displaying onset decomposition temperatures ( T d ) at around 250 °C. DSC measurements upon heating and cooling confirmed that OH terminated Janus dendrimers featuring large polarity difference in opposite …

catena-Poly[benzyltriethylammonium [tri-μ-thiocyanato-κ4N:S;κ2S:N-cadmate(II)]]

The title compound, {[(C6H5CH2)N(C2H5)3][Cd(SCN)3]}n, contains benzyl­triethyl­ammonium cations lying between one-dimensional chains of stoichiometry {[Cd(SCN)3]−}n. Each Cd2+ ion is 3N,3S-hexa­coordinated by thio­cyanate ligands in an octa­hedral arrangement. The asymmetric unit contains one cation and one anion.

Transition metal ion induced hydrogelation by amino-terpyridine ligands

Hydrogelation behavior of a new class of terpyridine based metallogelators are explored. The gelation and the gel morphology was found to be critically dependent on divalent metal ions, anions and on subtle structural changes on the gelator molecule.

Poly(alkylidenamines) dendrimers as scaffolds for the preparation of low-generation ruthenium based metallodendrimers

The aim of this article is to highlight the use of nitrile-functionalized poly(alkylidenamines) dendrimers as building blocks for the preparation of low-generation ruthenium based cationic metallodendrimers having in view potential biomedical applications. Air-stable poly(alkylidenamines) nitrile dendrimers, peripherally functionalized with the ruthenium moieties [Ru(η5-C5H5)(PPh3)2]+ or [RuCl(dppe)2]+, have been prepared, characterized and are being studied for their anticancer activity. The followed strategy is based on the biological advantages associated with low-generation dendrimers, the known activity of ruthenium compounds as anticancer drugs and the stability of these dendrimers at…

Spin Switching with Triazolate-Strapped Ferrous Porphyrins

Fe(III) porphyrins bridged with 1,2,3-triazole ligands were synthesized. Upon deprotonation, the triazolate ion coordinates to the Fe(III) ion, forming an overall neutral high-spin Fe(III) porphyrin in which the triazolate serves both as an axial ligand and as the counterion. The second axial coordination site is activated for coordination and binds p-methoxypyridine, forming a six-coordinate low-spin complex. Upon addition of a phenylazopyridine as a photodissociable ligand, the spin state of the complex can be reversibly switched with ultraviolet and visible light. The system provides the basis for the development of switchable catalase- and peroxidase-type catalysts and molecular spin sw…

The pentafluorophenyl group as π-acceptor for anions: a case study

Chemical science 6(1), 354-359 (2015). doi:10.1039/C4SC02762K

Self-assembly by co-ordination and strong hydrogen bonding. X-ray crystal structures of a dimeric trisodium complex of a new acidic complexing ligand and its dihydrate

Abstract The new acidic complexing ligand triethanolamine-O,O,O-triacetic acid, 3, is synthesized by reaction of triethanolamine with chloroacetic acid in the presence of sodium tert-butoxide. The resulting Na complex, 4, and its dihydrate, 5, contain two ligand molecules, both with one Na+ ion interaction and both co-ordinated to a third, central, Na+ ion. In addition the acidic ligands are hydrogen bonded to each other, like carboxylic acids, and in 4, by three crystallographically symmetric hydrogen bonds, while in 5, due to the breakdown of symmetry, two normal and one crystallographically symmetrical hydrogen bond. Inside this extraordinary dimeric assembly (a pseudo-cryptate) are the …

Synthesis, structural diversity, inter-conversion and reactivity of Cu(II) complexes of hydroxy-rich molecules

Tetranuclear Cu(II) complexes having linear, cubane and pseudodouble-cubane cores were synthesized using hydroxy-rich molecules possessing amine and imine groups. The products were structurally characterized and were studied for their ability to oxidize catechol as well as for their inter-conversion between mono- and tetra-nuclear complexes.

Ion Pair Recognition of Quaternary Ammonium and Iminium Salts by Uranyl-Salophen Compounds in Solution and in the Solid State

Efficient ditopic receptors for quaternary ammonium and iminium salts have been obtained upon functionalization of the uranyl-salophen unit with conformationally flexible side arms bearing phenyl or beta-naphthyl substituents. Binding affinities in chloroform solution have been measured for a large number of quaternary salts comprising tetramethylammonium (TMA), tetrabutylammonium (TBA), acetylcholine (ACh), N-methylpyridinium (NMP), and N-methylisoquinolinium (NmiQ) cations. Recognition of the anion partner is ensured by coordination to the hard Lewis acidic uranyl center, whereas cation-pi/CH-pi interactions of the quaternary ions are established with the aromatic pendants. The role of th…

Simultaneous Endo- and Exo-Complex Formation of Pyridine[4]arene Dimer with Neutral and Anionic Guests

The formation of complexes between hexafluorophosphate (PF6−) and tetraisobutyloctahydroxypyridine[4]arene has been thoroughly studied in the gas phase (ESI‐QTOF‐MS, IM‐MS, DFT calculations), in the solid state (X‐ray crystallography), and in chloroform solution (1H, 19F, and DOSY NMR spectroscopy). In all states of matter, simultaneous endo complexation of solvent molecules and exo complexation of a PF6− anion within a pyridine[4]arene dimer was observed. While similar ternary complexes are often observed in the solid state, this is a unique example of such behavior in the gas phase. peerReviewed

An ab Initio MO Study of Silver Triflate Complexation in [2.2.1]Cyclophane π-Prismands

Ab initio Hartree-Fock and DFT MO calculations have been used to study the conformations of six [2.2.1]cyclophane π-prismands and the formation of their π-complexes with silver triflate (AgSO 3 CF 3 ). The lowest energy cyclophane conformations and their silver triflate π-complexes have been calculated with HF/3-21G* and B3LYP/3-21G* levels of theory. The nature of bonding in silver triflate π-complexes has been studied with natural bond orbital analysis (NBO). Energies of the calculated cyclophanes and complexes, together with the formation energies of those complexes, have also been discussed. The results have been compared to available X-ray crystal structures and also to results of the …

Neutral Organometallic Halogen Bond Acceptors: Halogen Bonding in Complexes of PCPPdX (X = Cl, Br, I) with Iodine (I(2)), 1,4-Diiodotetrafluorobenzene (F4DIBz), and 1,4-Diiodooctafluorobutane (F8DIBu).

The behavior of a sterically crowded neutral pincer {2,6-bis[(di-t-butylphosphino)methyl]-phenyl}palladium (PCPPd) halides, PCPPdX (X = Cl, Br or I), as XB acceptors with strong halogen bond (XB) donors, iodine (I2), 1,4-diiodotetrafluorobenzene (F4DIBz), and 1,4-diiodooctafluorobutane (F8DIBu) were studied in the solid state. The co-crystallization experiments afforded high-quality single crystals of XB complexes PCPPdCl–I2 (1a), PCPPdBr–I2 (2a), PCPPdI–I2(3a), PCPPdCl–F4DIBz (1b), PCPPdBr–F4DIBz (2b), and PCPPdBr–F8DIBu (2c). The 1:1 iodine complexes (1a, 2a, and 3a) all showed a strong halogen bonding interaction, the reduction of the sum of the van der Waals radii of halogen to iodine b…

The inherent structural instability: concentration-dependent transformation of pyrogallarene to pyrogallarene lactones.

Pyrogallarene shows concentration-dependent instability in dilute solutions resulting in elimination of two ketene molecules and formation of pyrogallarene lactones. This unexpected phenomenon, which is not observed with resorcinarenes, highlights the significance of the four hydroxyl groups at 2-position for the molecular characteristics of pyrogallarenes.

Selective Encapsulation and Enhancement of the Emission Properties of a Luminescent Cu(I) Complex in Mesoporous Silica

Surprising solvent-induced structural rearrangements in large [N⋯I+⋯N] halogen-bonded supramolecular capsules

Coordinative halogen bonds have recently gained interest for the assembly of supramolecular capsules. Ion mobility-mass spectrometry and theoretical calculations now reveal the well-defined gas-phase structures of dimeric and hexameric [N...I+...N] halogen-bonded capsules with counterions located inside their cavities as guests. The solution reactivity of the large hexameric capsule shows the intriguing solvent-dependent equilibrium between the hexamer and an unprecedented pentameric [N...I+...N] halogen-bonded capsule, when the solvent is changed from chloroform to dichloromethane. The intrinsic flexibility of the cavitands enables this novel structure to adopt a pseudo-trigonal bipyramida…

Concave π-prismand hydrocarbon [2.2.2]cyclophanes and their crystalline Ag-triflate complexes

New small concave hydrocarbon cyclophanes were prepared via the well-known HD-2SO2-method. The cyclophanes obtained are isomers of the very well-known [2.2.2]p,p,p-cyclophane, C24H24, a π-prismand efficiently complexing Ag+-ion. X-ray crystal structure determinations showed the bis-sulfide 7 (1,10-dithia[3.3.2]m,p,p-cyclophane) to be helically chiral and that the conformation of the parent hydrocarbon cyclophane 13 ([2.2.2]m,p,p-cyclophane) does not change dramatically upon complexation with the Ag+-ion. The 16- and 17-membered [2.2.2]m,m,p- and [2.2.2]m,p,p-cyclophane (15 and 16) also act as π-prismands and form surprisingly similar crystalline 1:1 Ag-triflate complexes (π-prismates) as th…

Water Structure Recovery in Chaotropic Anion Recognition: High-Affinity Binding of Dodecaborate Clusters to γ-Cyclodextrin

Dodecaborate anions of the type B12X12(2-) and B12X11Y(2-) (X=H, Cl, Br, I and Y=OH, SH, NH3(+), NR3(+)) form strong (K(a) up to 10(6) L mol(-1), for B12Br12(2-)) inclusion complexes with γ-cyclodextrin (γ-CD). The micromolar affinities reached are the highest known for this native CD. The complexation exhibits highly negative enthalpies (up to -25 kcal mol(-1)) and entropies (TΔS up to -18.4 kcal mol(-1), both for B12I12(2-)), which position these guests at the bottom end of the well-known enthalpy-entropy correlation for CDs. The high driving force can be traced back to a chaotropic effect, according to which chaotropic anions have an intrinsic affinity to hydrophobic cavities in aqueous …

Three 2,5-dialkoxy-1,4-diethynylbenzene derivatives

2,5-Dieth­oxy-1,4-bis­[(trimethyl­silyl)ethyn­yl]benzene, C20H30O2Si2, (I), constitutes one of the first structurally characterized examples of a family of compounds, viz. the 2,5-dialk­oxy-1,4-bis­[(trimethyl­silyl)ethyn­yl]benzene derivatives, used in the preparation of oligo(phenyl­ene­ethynylene)s via Pd/Cu-catalysed cross-coupling. 2,5-Dieth­oxy-1,4-diethynylbenzene, C14H14O2, (II), results from protodesilylation of (I). 1,4-Diethynyl-2,5-bis­(hept­yloxy)benzene, C24H34O2, (III), is a long alk­yloxy chain analogue of (II). The molecules of compounds (I)–(III) are located on sites with crystallographic inversion symmetry. The large substituents either in the alkynyl group or in the benz…

Luminescent alkynyl-gold(i) coumarin derivatives and their biological activity

The synthesis and characterization of three propynyloxycoumarins are reported in this work together with the formation of three different series of gold(i) organometallic complexes. Neutral complexes are constituted by water soluble phosphines (PTA and DAPTA) which confer water solubility to them. The X-ray crystal structure of 7-(prop-2-in-1-yloxy)-1-benzopyran-2-one and its corresponding dialkynyl complex is also shown and the formation of rectangular dimers for the gold derivative in the solid state can be observed. A detailed analysis of the absorption and emission spectra of both ligands and complexes allows us to attribute the luminescent behaviour to the coumarin organic ligand. More…

An Unlockable-Relockable Iron Cage by Subcomponent Self-Assembly

Self-assembly of metallosupramolecular rhombi from chiral concave 9,9'-spirobifluorene-derived bis(pyridine) ligands.

Two new 9,9’-spirobifluorene-based bis(4-pyridines) were synthesised in enantiopure and one also in racemic form. These ligands act as concave templates and form metallosupramolecular [(dppp)2M2L2] rhombi with cis-protected [(dppp)Pd]2+ and [(dppp)Pt]2+ ions. The self-assembly process of the racemic ligand preferably occurs in a narcissistic self-recognising manner. Hence, a mixture of all three possible stereoisomers [(dppp)2M2{(R)-L}2](OTf)4, [(dppp)2M2{(S)-L}2](OTf)4, and [(dppp)2M2{(R)-L}{(S)-L}](OTf)4 was obtained in an approximate 1.5:1.5:1 ratio which corresponds to an amplification of the homochiral assemblies by a factor of approximately three as evidenced by NMR spectroscopy and m…

Bifunctional coordination polymers as efficient catalysts for carbon dioxide conversion

Alkali metal mediated resorcarene capsules: An ESI-FTICRMS study on gas-phase structure and cation binding of tetraethyl resorcarene and its per-methylated derivative

AbstractElectrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) with additional ab initio calculations were used to examine the alkali metal cation binding selectivity (i.e., molecular recognition) and host properties of tetraethyl resorcarene (1) and its per-methylated derivative (2). The significance of intramolecular hydrogen bonding for the crown conformation was demonstrated. The presence of intramolecular flip-flop hydrogen bonding in 1 was confirmed both with calculations and in ND3-exchange experiments. All the alkali metal cations formed host–guest complexes by docking inside the cavity of the host. Complexation with the larger cations, esp…

Ein achtkerniger metallosupramolekularer Würfel mit Spin-Crossover-Eigenschaften

Formation and trapping of the thermodynamically unfavoured inverted-hemicucurbit[6]uril

Amplification of a thermodynamically unfavoured macrocyclic product through the directed shift of the equilibrium between dynamic covalent chemistry library members is difficult to achieve. We show for the first time that during condensation of formaldehyde and cis-N,N'-cyclohexa-1,2-diylurea formation of inverted-cis-cyclohexanohemicucurbit[6]uril (i-cis-cycHC[6]) can be induced at the expense of thermodynamically favoured cis-cyclohexanohemicucurbit[6]uril (cis-cycHC[6]). The formation of i-cis-cycHC[6] is enhanced in low concentration of the templating chloride anion and suppressed in excess of this template. We found that reaction selectivity is governed by the solution-based template-a…

Self-assembling resorcinarene capsules: solid and gas phase studies on encapsulation of small alkyl ammonium cations

The self-assembling process of unsubstituted resorcinarenes (1, 2 and 3) to dimeric capsules encapsulating small tetra-alkyl ammonium cations 4–7 has been studied in solid and gaseous states by X-ray crystallographic and mass spectrometric methods. Hydrogen bonding and cation-π interaction as well as the proper encapsulation in the empty cavity of the capsule appear to be the most important interactions in the capsule formation process. Competitive mass spectrometric studies clearly indicated preference of the tetramethyl ammonium cation (4) over tetraethyl ammonium cation (6) and especially tetrabutyl ammonium cation (7). The crystal structures of altogether eight dimeric capsules of resor…

ChemInform Abstract: Asymmetric Synthesis of Cyclopentanes Bearing Four Contiguous Stereocenters via an NHC-Catalyzed Michael/Michael/Esterification Domino Reaction.

An NHC-catalyzed Michael/Michael/esterification domino reaction via homoenolate/enolate intermediates for the asymmetric synthesis of tetrasubstituted cyclopentanes bearing four contiguous stereocenters is described. A variety of α,β-unsaturated aldehydes and 2-nitroallylic acetates react well with good domino yields and high stereoselectivities.

N-(2,3,5,6-Tetrafluoropyridyl)sulfoximines: synthesis, X-ray crystallography, and halogen bonding

In the presence of KOH, NH-sulfoximines react with pentafluoropyridine to give N-(tetrafluoropyridyl)sulfoximines (NTFP-sulfoximines) in moderate to excellent yields. Either a solution-based or a superior solvent-free mechanochemical protocol can be followed. X-Ray diffraction analyses of 26 products provided insight into the bond parameters and conformational rigidity of the molecular scaffold. In solid-state structures, sulfoximines with halo substituents on the S-bound arene are intermolecularly linked by C–X⋯OS (X = Cl, Br) halogen bonds. Hirshfeld surface analysis is used to assess the type of non-covalent contacts present in molecules. For mixtures of three different S-pyridyl-substit…

N-Cinnamoyltetraketide Derivatives from the Leaves of Toussaintia orientalis

Seven N-cinnamoyltetraketides (1−7), including the new Ztoussaintine E (2), toussaintine F (6), and toussaintine G (7), were isolated from the methanol extract of the leaves of Toussaintia orientalis using column chromatography and HPLC. The configurations of E-toussaintine E (1) and toussaintines A (3) and D (5) are revised based on single-crystal X-ray diffraction data from racemic crystals. Both the crude methanol extract and the isolated constituents exhibit antimycobacterial activities (MIC 83.3−107.7 μM) against the H37Rv strain of Mycobacterium tuberculosis. Compounds 1, 3, 4, and 5 are cytotoxic (ED50 15.3−105.7 μM) against the MDA-MB-231 triple negative aggressive breast cancer cel…

Inclusion complexes of Cethyl-2-methylresorcinarene and pyridine N-oxides: breaking the C–I⋯−O–N+ halogen bond by host–guest complexation

C ethyl-2-Methylresorcinarene forms host–guest complexes with aromatic N-oxides through multiple intra- and intermolecular hydrogen bonds and C–H⋯π interactions. The host shows conformational flexibility to accommodate 3-methylpyridine N-oxide, while retaining a crown conformation for 2-methyl- and 4-methoxypyridine N-oxides highlighting the substituent effect of the guest. N-Methylmorpholine N-oxide, a 6-membered ring aliphatic N-oxide with a methyl at the N-oxide nitrogen, is bound by the equatorial −N–CH3 group located deep in the cavity. 2-Iodopyridine N-oxide is the only guest that manifests intermolecular N–O⋯I–C halogen bond interactions, which are broken down by the host resulting i…

Complexation behaviour of hexadentate ligands possessing N2O4and N2O2S2cores: differential reactivity towards Co(ii), Ni(ii) and Zn(ii) salts and structures of the products

Reactions of divalent metal salts of Co, Ni and Zn with 1,2-di(salicylaldimino-o-phenylthio) ethane (H2L1) and 1,2-di(naphthaldimino-o-phenylthio) ethane (H2L2), having N2O2S2 cores, and 1,2-di(O-salicylaldimino-o-hydroxyphenyl) ethane (H2L3), having a N2O4 core, have been explored. Out of the three ligands and the nine products obtained from the corresponding reactions, two ligands and seven products were crystallographically characterized. However, all the ligands and the products were characterized by analytical and spectral methods. Reaction of H2L1 and H2L2 with Co(II) salts results in oxidative cleavage of the C-S bond to produce a Co(III) product bound to two dissimilar tridentate li…

Cyclic [2]Pseudorotaxane Tetramers Consisting of Two Rigid Rods Threaded through Two Bis-Macrocycles: Copper(I)-Templated Synthesis and X-ray Structure Studies

Variously substituted coordinating rigid rods have been synthesized which incorporate a central 4,7-phenanthroline nucleus attached to two 2-pyridyl groups via its 3 and 8 positions, so as to yield bis-bidentate chelates, the two-coordinating axes of the chelates being parallel to one another. Regardless of the nature of the substituents borne by the rods, the copper(I)-induced threading reaction of two such rods through the rings of two bis-macrocycles affords in a quantitative yield the 4-copper(I) threaded assembly. The [2]pseudorotaxane tetramers thus obtained have been fully characterized in solution and, for one of them, an X-ray structure could be obtained, confirming the threaded na…

Hierarchical, Lithium‐Templated Assembly of Helicate‐Type Complexes: How Versatile Is This Reaction?

Catechol ligands that bear carbonyl functions such as esters or aldehydes in the 3-position (1a–c-H2) form triple-stranded, helicate-type complexes [Li3(1a–c)6Ti2]– with titanium(IV) and the corresponding double-stranded compounds [Li2(1a–c)4B2] with boron(III) in hierarchical, lithium-templatedprocesses. The related 8-hydroxyquinoline ligands 2a,b-H can be used for the formation of similar complexes[Li3(2a,b)6M2]+ with cobalt(II), nickel(II), or zinc(II). A prerequisite for the formation of the lithium-bridged dimers is a negative charge of the mononuclear complexes, which are able to electrostatically attract the lithium cations and thus compensate the repulsion between the cations. (© Wi…

Self-ordering of metallogrid complexes via directed hydrogen-bonding.

Reaction of imidazole aldehydes with dihydrazino derivatives of 2-phenylpyrimidine provides a family of bis(acylhydrazone) ligands which form [2 × 2] metallogrid complexes with transition metal ions including Fe(II), Co(II), Cu(II) and Zn(II). The free ligands show H-bonding interactions, both donor and acceptor, largely involving the imidazole units, while binding of the metal ions occupies all the acceptor sites and leaves only the pyrrolic-NH site as an H-bond donor, although its deprotonation by a strong base can regenerate an acceptor. These H-bonding interactions have been studied by (1)H NMR spectroscopy in solution and in the solid state by means of several crystal structure determi…

Sharing the salt bowl: counterion identity drives N-alkyl resorcinarene affinity for pyrophosphate in water

N-Alkyl ammonium resorcinarene chloride receptors, NARX4, have been shown to act as high-sensitivity detectors of pyrophosphate (PPi), a biomarker of disease, in aqueous media through the chloride-to-PPi exchange [NAR(Cl)4 to NARPPi]. The nature of the anion of the macrocyclic NARX4 (X = Cl−, Br−, triflate OTf−) receptor greatly influences the PPi-affinity in aqueous media. The binding affinity for [NAR (Cl)4] is 3.61 × 105 M−1, while the NAR (Br)4 and NAR (OTf)4 show stronger binding of 5.30 × 105 M−1, and 6.10 × 105 M−1, respectively. The effects of upper rim ammonium cation, –N+H2R substituents (R = 3-hydroxypropyl, cyclohexyl, benzyl, or napththalen-1-ylmethyl), of the macrocyclic resor…

ChemInform Abstract: Poly(alkylidenamines) Dendrimers as Scaffolds for the Preparation of Low-Generation Ruthenium Based Metallodendrimers

The aim of this article is to highlight the use of nitrile-functionalized poly(alkylidenamines) dendrimers as building blocks for the preparation of low-generation ruthenium based cationic metallodendrimers having in view potential biomedical applications. Air-stable poly(alkylidenamines) nitrile dendrimers, peripherally functionalized with the ruthenium moieties [Ru(η5-C5H5)(PPh3)2]+ or [RuCl(dppe)2]+, have been prepared, characterized and are being studied for their anticancer activity. The followed strategy is based on the biological advantages associated with low-generation dendrimers, the known activity of ruthenium compounds as anticancer drugs and the stability of these dendrimers at…

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Dynamic formation of hybrid peptidic capsules by chiral self-sorting and self-assembly.

Owing to their versatility and biocompatibility, peptide-based self-assembled structures constitute valuable targets for complex functional designs. It is now shown that artificial capsules based on β-barrel binding motifs can be obtained by means of dynamic covalent chemistry (DCC) and self-assembly. Short peptides (up to tetrapeptides) are reversibly attached to resorcinarene scaffolds. Peptidic capsules are thus selectively formed in either a heterochiral or a homochiral way by simultaneous and spontaneous processes, involving chiral sorting, tautomerization, diastereoselective induction of inherent chirality, and chiral self-assembly. Self-assembly is shown to direct the regioselectivit…

Metallogel formation in aqueous DMSO by perfluoroalkyl decorated terpyridine ligands.

Terpyridine based ligands 1 and 2, decorated with a C8F17 perfluorinated tag, are able to form stable thermoreversible gels in the presence of several d-block metal chloride salts. The gel systems obtained have been characterized by NMR, X-ray diffraction, electron microscopies and Tgel experiments in order to gain insights into the observed different behaviour of the two similar ligands, also in terms of the effect of additional common anionic species. peerReviewed

Generation of [2×2] Grid Metallosupramolecular Architectures from Preformed Ditopic Bis(acylhydrazone) Ligands and through Component Self‐Assembly

Ditopic bis(acylhydrazone) ligands, derived from the reactions of carbohydrazides with 2-phenylpyrimidine-4,6-dicarbaldehyde and designed for grid formation with octahedrally coordinating transition-metal ions, exhibit a varied coordination chemistry depending upon the degree of their deprotonation. The neutral acylhydrazones are relatively poor ligands and are seemingly involved in multiple, labile complexation equilibria varying with the solvent and the particular metal salt in solution; nevertheless, grid complexes of different forms can be isolated in the solid state. Although only limited study has been made of the singly deprotonated ligands, grid species appear to be much more readil…

Effect of Gold(I) on the Room-Temperature Phosphorescence of Ethynylphenanthrene.

The synthesis of two series of gold(I) complexes containing the general formulae PR 3 ‐Au‐C≡C‐phenanthrene (PR 3 = PPh 3 ( 1a / 2a ), PMe 3 ( 1b / 2b ), PNaph 3 ( 1c / 2c )) or (diphos)(Au‐C≡C‐phenanthrene) 2 (diphos = 1,1‐ bis (diphenylphosphino)methane, dppm ( 1d / 2d ); 1,4‐ bis (diphenylphosphino)butane, dppb ( 1e / 2e )) have been synthesized. The two series differ on the position of the alkynyl substituent on the phenanthrene chromophore, being at the 9‐position (9‐ethynylphenanthrene) for the L1 ‐series and at the 2‐position (2‐ethynylphenanthrene) for the L2 ‐series. The compounds have been fully characterized by 1 H and 31 P NMR and IR spectroscopy, mass spectrometry and single cry…

Protonation-induced fluorescence modulation of carbazole-based emitters

The development of purely organic fluorescence emitters is of great importance for their low cost and high performance. Responding to this demand, carbazole is a promising emitter due to its extensive freedom for functionalisation, high thermal and chemical stability, as well as low cost. Herein, the effect of protonation on the fluorescence of various pyridine-functionalised carbazole-based bipolar host materials was studied both in solution and in the solid-state. The restriction of intramolecular rotation of the molecules upon protonation of the pyridyl-moiety together with easier planarization of the protonated acceptor and the donor moieties and relocalisation of the LUMO orbital on th…

Host–guest complexes of conformationally flexible C-hexyl-2-bromoresorcinarene and aromatic N-oxides: solid-state, solution and computational studies

Host–guest complexes of C-hexyl-2-bromoresorcinarene (BrC6) with twelve potential aromatic N-oxide guests were studied using single crystal X-ray diffraction analysis and 1H NMR spectroscopy. In the solid state, of the nine obtained X-ray crystal structures, eight were consistent with the formation of BrC6-N-oxide endo complexes. The lone exception was from the association between 4-phenylpyridine N-oxide and BrC6, in that case the host forms a self-inclusion complex. BrC6, as opposed to more rigid previously studied C-ethyl-2-bromoresorcinarene and C-propyl-2-bromoresorcinarene, undergoes remarkable cavity conformational changes to host different N-oxide guests through C–H···π(host) intera…

An unusual magnetic response in a π-stacked 66-dia net structure of [4 + 2] copper(II) cubane

A phenoxo bridged antiferromagnetic copper(II) cubane features a π-stacked 66-dia net framework and creates long range ferromagnetic ordering, as evidenced from a coercivity maximum (∼2000 Oe) at 20 K with very unusual saturation magnetization.

Iodination of antipyrine with [N–I–N]+ and carbonyl hypoiodite iodine(i) complexes

A series of iodine(I) complexes, both known and new, were synthesised and the dependence of iodination reactivity on the identity of the Lewis bases and anions present was investigated. Using a previously established screening protocol based on the iodination of antipyrine to iodo-antipyrine, the capability of the iodine(I) species to perform the iodination was tested and compared, especially in relation to Barluenga's reagent, [I(pyridine)2]BF4. The results indicated that the identity of both the Lewis bases and the anion influence the iodination capability of the iodine(I) species, and that the less efficient reagents can deliver favourably comparable percentage conversions with longer re…

Chiral donor–π-acceptor azobenzene dyes

Abstract Four chiral donor–π-acceptor azobenzene dye conjugates were synthesized and characterized. Chiral moieties, namely (S)-(+)-2-(6-methoxy-2-naphthyl)propionic acid (naproxen) and (S)-2-aminopropionic acid ( l -alanine), were attached to either the donor end or the acceptor site of the azo compound using ester or amide bonds, respectively. The structures of the molecules were verified using 1H NMR, 13C NMR and ESI TOF mass spectrometry; spectral properties were evaluated with UV–vis and CD spectrometry whilst thermal stability was determined by TGA. The compounds displayed a broad absorption maximum in the visible region between 433 and 483 nm. All compounds showed relatively high the…

Alternative Motifs for Halogen Bonding

The halogen-bonding interaction is one of the rising stars in supramolecular chemistry. Although other weak interactions and their influence on the structure and chemistry of various molecules, complexes and materials have been investigated thoroughly, the field of halogen bonding is still quite unexplored and its impact on chemistry in general is yet to be fully revealed. In principle, every Y–X bond (Y = electron-withdrawing atom or moiety, X = halogen atom) can act as a halogen-bond donor when the halogen is polarized enough by Y. Perfluorohalocarbons are iconic halogen-bond donor molecules in which Y is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. In this art…

Single-Crystal X-ray Diffraction and Solution Studies of Anion-π Interactions inN-(Pentafluorobenzyl)pyridinium Salts

A solid-state structural study on anion–π interaction in various N-(pentafluorobenzyl)pyridinium salts accompanied by NMR spectroscopic investigations is presented. The crystal structures of 1a–1d reveal different kinds of contacts with anions, including anion–π interactions. In particular, the solid-state structure of 1b-I3 shows distinct evidence of anion–π interactions. Attempts to study anion–π interactions in solution were not successful, but their presence in solution could not be ruled out.

The Difficult Marriage of Triarylcorroles with Zinc and Nickel Ions.

The coordination chemistry of corrole has witnessed a great improvement in the past few years and its Periodic Table has been widened to be so large that it is compared with that of porphyrins. However, Ni and Zn ions, commonly used with porphyrins for both synthetic and theoretical purposes, are sparsely reported in the case of corroles. Here, we report synthetic protocols for preparing Ni and Zn triarylcorrole complexes. In the case of Zn, the preliminary oxidation of the free base corrole in DMSO to the neutral corrole radical is a necessary step to obtain the coordination of the metal ion, because the direct reaction led to the formation of an open-chain tetrapyrrole. The Ni complex cou…

The C–I···–O–N+ Halogen Bonds with Tetraiodoethylene and Aromatic N-Oxides

The nature of C–I⋯⁻O–N⁺ interactions, first of its kind, between non-fluorinated tetraiodoethylene XB-donor and pyridine N-oxides (PyNO) are studied by single-crystal X-ray diffraction (SCXRD) and ...

Efficient stabilisation of a dihydrogenphosphate tetramer and a dihydrogenpyrophosphate dimer by a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties

A cyclic pseudooctapeptide 2 is described containing 1,4-disubstituted 1,2,3-triazole moieties. This compound features eight converging hydrogen bond donors along the ring, namely four amide NH and four triazole CH groups, which enable 2 to engage in interactions with anions. While fully deprotonated sulfate anions exhibit only moderate affinity for 2, protonated anions such as dihydrogenpyrophosphate and dihydrogenphosphate anions are strongly bound. Complexation of the phosphate-derived anions involves sandwiching of a dihydrogenpyrophosphate dimer or a dihydrogenphosphate tetramer between two pseudopeptide rings. X-ray crystallography provided structural information, while 1H NMR spectro…

Crystal structure of 4,6-O-ethylidene-N-(2-hydroxybenzylidene)-β-D-glucopyranosylamine

4,6-O-Ethylidene-N-(2-hydroxybenzylidene)-β-D-glucopyranosylamine was synthesized and characterized using analytical, spectral and single-crystal X-ray diffraction methods. The anomeric nature of the saccharide moiety was proposed based on 1H NMR studies and was confirmed by the crystal structure. The lattice structure of this compound was compared with that of its analogues.

Cytotoxicity and NMR Studies of Platinum Complexes with Cyclooctadiene Ligands

The synthesis of a series of platinum complexes containing cyclooctadiene ligands with the general structure PtMeL(R-cod) (where L = Cl, I, nC3F7, iC3F7, nC8F17, Me, aryl, alkynyl and R = H, Me, Et, iPr, nBu, iBu, nHex, Ph) is presented. All complexes are remarkably stable and were obtained in excellent yields. Their structure in both solution and the solid state were explored by crystal structures and multinuclear (1H, 13C, 19F, 195Pt) NMR spectroscopy. Cytotoxicity experiments with selected complexes in HeLa cells revealed higher toxicity in comparison to that of cisplatin for most of the structures.

Model studies on a diastereoselective synthesis of the C(33)–C(37) fragment of Amphotericin B

Abstract A new, short and highly diastereoselective synthetic route aiming at the C(33)–C(37) fragment of Amphotericin B has been developed. Studies with a model aldehyde (benzaldehyde) have given very promising results: the desired stereochemistry of all four stereocenters of the target molecule has been achieved with high diastereoselection. The stereochemistry of three key intermediates and the target segment has been confirmed by X-ray crystallography.

From attraction to repulsion : anion–π interactions between bromide and fluorinated phenyl groups

Anion–π interactions in crystals of fluorobenzyl ammonium salts depend on the degree of fluorination at the aromatics.

cis-Aquabis[bis(diphenylphosphino)ethane-κ2 P,P′]chlororuthenium(II) hexafluorophosphate dichloromethane sesquisolvate hemihydrate

In the title compound, [RuCl(C26H24P)2(H2O)]PF6·1.5CH2Cl2·0.5H2O, the complex RuII cation is in a slightly distorted octahedral environment, chelated by two bis(diphenylphosphino)ethane ligands, with a water molecule and a chloride anion in a mutually cis geometry completing the coordination.

Thermal and X-ray powder diffraction studies of aliphatic polyester dendrimers

The syntheses and thermal and X-ray powder diffraction analyses of three sets of aliphatic polyester dendrimers based on 2,2-bis(hydroxymethyl)propionic acid as a repeating unit and 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, and 1,1,1-tris(hydroxymethyl)ethane as core molecules are reported. These dendritic polyesters were prepared in high yields with the divergent method. The thermal properties of these biodendrimers were evaluated with thermogravimetric analysis and differential scanning calorimetry. The thermal decomposition of the compounds occurred around 250 °C for the hydroxyl-ended dendrimers and around 150 °C for the acetonide-protected dendrimers. In addition, the crystallinit…

The role of cation⋯π interactions in capsule formation: co-crystals of resorcinarenes and alkyl ammonium salts

An unprecented dimeric capsular assembly of a tetramethylated C-hexyl resorcinarene and an expected one from unsubstituted C-butyl resorcinarene with tetramethylammonium cation are described. Surprisingly tetramethylated C-hexyl resorcinarene, with no apparent possibility for intra-capsular hydrogen bonds, forms a capsule which is held together solely by the cation⋯π interactions and the complementary geometry of the spherical guest cation and the concave resorcinarene host. The C-butyl resorcinarene capsule, as in the case of dimeric resorcinarene capsules reported earlier, is mediated viasolvent molecules and intra-capsular hydrogen bonds. We also report here two co-crystals of C-methyl r…

Enantioselective Total Syntheses of (+)-Hippolachnin A, (+)-Gracilioether A, (-)-Gracilioether E, and (-)-Gracilioether F.

The Plakortin polyketides represent a structurally and biologically fascinating class of marine natural products. Herein, we report a unified strategy that enables the divergent syntheses of various Plakortin polyketides with high step-economy and overall efficiency. As proof-of-concept cases, the enantioselective total syntheses of (+)-hippolachnin A, (+)-gracilioether A, (-)-gracilioether E, and (-)-gracilioether F have been accomplished based on a series of bio-inspired, rationally designed, or serendipitously discovered transformations, which include (1) an organocatalytic asymmetric 1,4-conjugate addition to assemble the common chiral γ-butenolide intermediate enroute to all of the afo…

Supramolecular Chirogenesis in Bis-Porphyrin: Crystallographic Structure and CD Spectra for a Complex with a Chiral Guanidine Derivative

The complexation of (3aR,7aR)-N-(3,5-bis(trifluoromethyl)phenyl)octahydro-2H-benzo[d]imidazol-2-imine (BTI), as a guest, to ethane-bridged bis(zinc octaethylporphyrin), bis(ZnOEP), as a host, has been studied by means of ultraviolet-visible (UV-Vis) and circular dichroism (CD) absorption spectroscopies, single crystal X-ray diffraction, and computational simulation. The formation of 1:2 host-guest complex was established by X-ray diffraction and UV-Vis titration studies. Two guest BTI molecules are located at the opposite sides of two porphyrin subunits of bis(ZnOEP) host, which is resting in the anti-conformation. The complexation of BTI molecules proceed via coordination of the imine nitr…

Halogen Bonded Analogues of Deep Cavity Cavitands

The first examples of halogen bonded analogues of deep cavity cavitands with guest binding properties, formed between N-alkyl ammonium resorcinarene halides as acceptors and bromotrichloromethane as the donor, are reported in the solid state and in solution.

Toward Near-Infrared Emission in Pt(II)-Cyclometallated Compounds: From Excimers’ Formation to Aggregation-Induced Emission

Two series of Pt(II)-cyclometallated compounds containing N^C^N tridentate and alkynyl-chromophore ligands have been synthesized and structurally characterized. The N^C^N ligands differ on the presence of R1 = H or F in the central aromatic ring, while six different chromophores have been introduced to the alkynyl moiety. Single-crystal X-ray structures for some of the compounds reveal the presence of weak intermolecular contacts responsible for the formation of some dimers or aggregates. The photophysical characterization shows the presence of two emission bands in solution assigned to the 3π–π* transition from the N^C^N ligands mixed with 3MLCT/3ILCT transitions (higher energy band) in de…

A linear Fe-O-Fe unit in bis(dibenzyldimethylammonium)-oxo-di[tribromoferrate(III)]

The title compound, (C16H20N)2[Fe2Br6O], crystallizes with one dibenzyl­dimethylammonium cation and one half of a [mu]-oxo-bis­[tribromo­ferrate(III)] anion in the asymmetric unit. The bridging oxo group is situated on an inversion centre, resulting in a linear conformation for the Fe-O-Fe unit. The iron(III) cations have tetra­hedral geometry, with bond angles in the range 106.8 (1)-112.2 (1)°. The ion pairs are held together by Coulombic forces and C-H...Br hydrogen bonds. Each Br- anion forms one hydrogen bond. No C-H...O hydrogen bonds are found between the O atom in the Fe-O-Fe unit and surrounding counter-cations, consistent with the linear configuration of the Fe-O-Fe unit. peerRevie…

Self-Sorting Effects in the Self-Assembly of Metallosupramolecular Rhombi from Chiral BINOL-Derived Bis(pyridine) Ligands

Four BINOL-based bis(4-pyridyl) ligands were synthesised in enantiopure and racemic form. These ligands form metallosupramolecular [(dppp)2M2L2] rhombi with cis-protected [(dppp)Pd]2+ and [(dppp)Pt]2+ ions. In principle, racemic ligands can self-assemble into three stereoisomeric rhombi. The degree of self-sorting in the self-assembly process crucially depends on the substitution pattern and the resulting bend angle of the V-shaped ligands as well as the degree of steric crowding within the assembly when racemic ligands are used. Thus, these processes either lead to homochiral assemblies in a narcissistic self-recognition manner, to heterochiral assemblies in a social self-discriminating ma…

N1-Functionalized Indole-Phosphane Oxazoline (IndPHOX) Ligands in Asymmetric Allylic Substitution Reactions

N-Functionalized IndPHOX ligands bearing various groups have been synthesized and the effects of the N1-substituent on the reaction rate, yield, and asymmetric induction in a palladium-catalyzed allylic substitution reaction are reported. The presence of an oxygen atom in the ligands, namely an N-MOM or N-THP group, led to enhancement of the enantioselectivity in the allylic amination reaction. In addition, a ligand with a chiral oxazoline ring at C-1 and a phosphane substituent at C-2 provided high enantioselectivity in good yield in an asymmetric allylic alkylation reaction.

Regio- and Stereoselective Chloro Sulfoximidations of Terminal Aryl Alkynes Enabled by Copper Catalysis and Visible Light

Advanced synthesis &amp; catalysis 2552-2556 (2021). doi:10.1002/adsc.202100162

Selective recognition of fluoride anion in water by a copper(II) center embedded in a hydrophobic cavity

The ability of a water-soluble pentacationic calix[6]arene-based CuII complex to bind anions in water has been explored. Quite remarkably, the complex exhibits strong and selective fluoride binding in the pH range of 6–7. The binding constant at pH 5.9 was evaluated to be 85 000 M−1, which is one of the highest values ever reported for a fluoride probe in water and at this pH. The complex also binds chloride ions, but 1000 times less efficiently. The combination of the calix[6]arene hydrophobic cavity with the CuII complex, presenting its labile site in the endo position, is the reason for the selective recognition process. The single crystal X-ray structure of the organo-soluble parent com…

ChemInform Abstract: Concave π-Prismand Hydrocarbon [2.2.2]Cyclophanes and Their Crystalline Ag-Triflate Complexes.

New small concave hydrocarbon cyclophanes were prepared via the well-known HD-2SO2-method. The cyclophanes obtained are isomers of the very well-known [2.2.2]p,p,p-cyclophane, C24H24, a π-prismand efficiently complexing Ag+-ion. X-ray crystal structure determinations showed the bis-sulfide 7 (1,10-dithia[3.3.2]m,p,p-cyclophane) to be helically chiral and that the conformation of the parent hydrocarbon cyclophane 13 ([2.2.2]m,p,p-cyclophane) does not change dramatically upon complexation with the Ag+-ion. The 16- and 17-membered [2.2.2]m,m,p- and [2.2.2]m,p,p-cyclophane (15 and 16) also act as π-prismands and form surprisingly similar crystalline 1:1 Ag-triflate complexes (π-prismates) as th…

Mit Donorzentren versehener korbförmiger Molekülhohlraum — Darstellung, Struktur, Eigenschaften

Basket-shaped Molecular Cavity-Containing Donor Centres — Synthesis, Structure, Properties The macrocyclic basket-shaped molecule 2, composed of three 4-donor-substituted pyridine units, is synthesized by cyclisation of the chloromethyl compound 7 with sulfonamide 8. The X-ray structure analysis of 2 gives an impression of the shape of the molecular basket. Furthermore it demonstrates that the toluenesulfonamide residues interlink, creating dimeric units of 2 in the crystal.

Solid State Structures of Amide-Substituted 8-Hydroxyquinoline Derivatives

Abstract The amide substituted 8-hydroxyquinoline derivatives 3 and 4 form, in the solid state, hydrogen bonded polymers. Polymeric 3 adopts a helical conformation while 4 forms a double-stranded ladder-type structure.

Multinuclear magnetic resonance study of 1,3,3-trimethylbicyclo [2.2.1]heptan-2-one (fenchone) oxime, its five monochloro derivatives and a dehydrochlorination product

Fenchone oxime, 5-exo-chlorofenchone oxime, 6-exo-chlorofenchone oxime, 7-anti-chlorofenchone oxime, 8-chlorofenchone oxime, 9-chlorofenchone oxime and a dehydrochlorination product of 10-chlorofenchone oxime were synthesized from fenchone and the corresponding chlorofenchones. The 1H, 13C and 17O NMR spectra of the oximes and the dehydrochlorination product were recorded. The NMR data were compared with the corresponding parameters obtained earlier for fenchone and monochlorofenchones in order to determine the differences between the carbonyl and oxime substituents from the NMR spectroscopic point of view, and to assign the stereochemistry of the oxime group. This stereochemistry could not…

Probing the guest-binding preference of three structurally similar and conformationally adaptive macrocycles.

A hybrid macrocycle was synthesized by combining the repeat units in oxatub[4]arene and zorb[4]arene, and its recognition behavior and conformational analysis were studied. Three structurally similar and conformationally adaptive macrocycles show different guest-binding selectivities and preferences even in a complex mixture containing three macrocycles and three guests.

Polyether-bridged cyclophanes incorporating bisphenol A units as neutral receptors for quats: synthesis, molecular structure and binding properties

Two novel neutral polyoxyethylene bridged cyclophanes (2a and 2b) incorporating bisphenol A units were synthesized and characterized by means of x-ray crystal structure determination. The binding properties of 2a and 2b toward tetramethylammonium, N-methylpyridinium, and acetylcholine cations were evaluated by means of 1H NMR spectroscopy. Consistent with indications provided by the molecular structure, the cavity in the basket-like cyclophanes is large enough to accommodate the given guest cations conveniently. Circumstantial evidence was obtained that 1,1,2,2-tetrachloroethane is too large to enter the cavity of the smaller cyclophane 2a, but can be included in the cavity of the larger cy…

Crotofolane Diterpenoids and Other Constituents Isolated from Croton kilwae

Six new crotofolane diterpenoids (1-6) and 13 known compounds (7-19) were isolated from the MeOH- CH2Cl2 (1:1, v/v) extracts of the leaves and stem bark of Croton kilwae. The structures of the new compounds were elucidated by extensive analysis of spectroscopic and mass spectrometric data. The structure of crotokilwaepoxide A (1) was confirmed by single -crystal X-ray diffraction, allowing for the determination of its absolute configuration. The crude extracts and the isolated compounds were investigated for antiviral activity against respiratory syncytial virus (RSV) and human rhinovirus type-2 (HRV-2) in HEp-2 and HeLa cells, respectively, for antibacterial activity against the Gram-posit…

Asymmetric Synthesis of Spiro β-Lactamsviaa Squaramide- Catalyzed Sulfa-Michael Addition/Desymmetrization Protocol

An efficient asymmetric synthesis of spirocyclohexenone β-lactams bearing three contiguous stereocenters has been achieved in moderate to good yields and high stereoselectivities. The protocol involves the combination of a squaramide-catalyzed sulfa-Michael addition under desymmetrization via a dynamic kinetic resolution of racemic 2,5-cyclohexadienones.

Templated synthesis of a large and flexible covalent porphyrinic cage bearing orthogonal recognition sites.

A large covalent cage incorporating two porphyrins attached by four long and flexible polyether chains each bearing two 3-pyridyl ligands was synthesized from a DABCO-templated olefin metathesis reaction. The X-ray structure of the cage with the DABCO coordinated inside the cavity to the two zinc(II) porphyrins reveals a highly symmetric structure.

Enantiomer Separation of Tris(2,2′-bipyridine)ruthenium(II): Interaction of a D3-Symmetric Cation with a C2-Symmetric Anion

A compound widely used in the separation of the enantiomers of Δ,Λ-[Ru(bipy)3]2+ (bipy = 2,2′-bipyridine) and originally described as “a curious lattice compound” with the formula Δ-[Ru(bipy)3]3[Sb2(R,R-tart)2]2I2·18H2O (tart = tetradeprotonated, carboxyl and hydroxyl, tartaric acid anion) has been crystallographically characterized as this species with a slightly higher degree of hydration (19.5H2O). The crystal lattice has a layered structure in which sheets containing Δ-[Ru(bipy)3]2+ cations and iodide anions alternate with those containing [Sb2(R,R-tart)2]2– anions and water. The role of the iodide ions, which lie in pseudohexagonal cavities formed by the array of three inequivalent but…

A New Structural Motif for an Enantiomerically Pure Metallosupramolecular Pd4L8Aggregate by Anion Templating

An enantiomerically pure BINOL-based bis(3-pyridyl) ligand 1 assembles into a homochiral [Pd4(1)8] complex upon coordination to tetravalent PdII ions. The formation of this aggregate is templated by two tetrafluoroborate counterions that are encapsulated in two peripheral cavities. The resulting structure is a new structural motif for this kind of metallosupramolecular assemblies that arranges the palladium ions in a distorted tetrahedral fashion and forces ligand 1 to adopt two different conformations. Both phenomena are unique and cause an overall three-dimensional structure that has another confined, chiral, and hydrophilic central cavity.

N-Heterocyclic Carbene Catalyzed [3+2] Cycloaddition of Enals with Masked Cinnamates for the Asymmetric One-Pot Synthesis of Adipic Acid Derivatives.

A novel short entry to 3,4-disubstituted adipic acids has been developed by employing an asymmetric NHC-catalyzed [3+2] cycloaddition of enals with masked cinnammates in moderate to good yields and high stereoselectivities. The synthetic utility of the protocol was demonstrated by the basic conversion of the masked cyclopentanone intermediates to 3S,4S-disubstituted adipic acid precursors of pharmaceutically important gababutins.

Synthesis and characterization of 4,6-O-butylidene-N-(2-hydroxybenzylidene)-beta-D-glucopyranosylamine: crystal structures of 4,6-O-butylidene-alpha-D-glucopyranose, 4,6-O-butylidene-beta-D-glucopyranosylamine and 4,6-O-butylidene-N-(2-hydroxybenzylidene)-beta-D-glucopyranosylamine

4,6-O-Butylidene-N-(2-hydroxybenzylidene)-β-D-glucopyranosylamine was synthesized and characterized using analytical, spectral and single-crystal X-ray diffraction methods. 1H and 13C NMR studies showed the presence of the β-anomer, which has also been confirmed by the crystal structure. The molecular structure of this compound showed the presence of the tridentate ONO ligation-core. Both precursors, 4,6-O-butylidene-α-D-glucopyranose and 4,6-O-butylidene-β-D-glucopyranosylamine were characterized using single crystal X-ray diffraction. The α-anomeric nature of the former and β-anomeric nature of the latter were proposed based on 1H NMR studies and were confirmed by determining the crystal …

Base-assisted synthesis of 4-pyridinate gold(I) metallaligands: a study of their use in self-assembly reactions

Made available in DSpace on 2021-06-25T12:16:58Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-05-06 Ministerio de Economia y Competitividad (MINECO/FEDER) of Spain Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) The synthesis of di- and tritopic gold(I) metallaligands of the type [(Au4-py)(2)(mu(2)-diphosphane)] (diphosphane = bis(diphenylphosphanyl)isopropane or dppip (1), 1,2-bis(diphenylphosphanyl)ethane or dppe (2), 1,3-bis(diphenylphosphanyl)propane or dppp (3) and 1,4-bis(diphenylphosphanyl)butane or dppb (4)) and [(Au4-py)(3)(mu(3)-triphosphane)] (triphosphane = 1,1,1-tris(diphenylphosph…

Molecular Encapsulation. Organic Reactions in Constrained Systems. Edited by Udo H. Brinker and Jean-Luc Miesset.

Dendritic Pyridine-Functionalized Polyesters and Their Polycationic Hydrogen Bonded Picrates:  Synthesis and X-ray Structural Study of Weak Hydrogen Bonding

Nicotinato and isonicotinato functionalized pentaerythritol and dipentaerythritol dendritic polyester compounds were synthesized. The compounds were crystallized, and the single-crystal structures were determined. Protonation by picric acid produced charged dendritic polyesters. Analysis of the role of weak hydrogen bonding CH···π and π···π interactions in the solid state was performed and compared to the corresponding benzoxy analogues which were also synthesized. The tetranicotinate 3b and tetrabenzoate 4 were found to have analogous structures, which in turn differ from the structure of the tetraisonicotinate 3c. The difference is attributed to the crucial role of CH···O and CH···N hydro…

N-Heterocyclic Carbene Catalyzed Quadruple Domino Reactions through α,β-Unsaturated Acyl Azolium Intermediates : Asymmetric Synthesis of Cyclopenta[c]chromenones

An N‐heterocyclic carbene catalyzed domino sequence via α,β‐unsaturated acyl azolium intermediates has been developed. This strategy provides a convenient enantioselective route to functionalized tricyclic coumarin derivatives and cyclopentanes. DFT studies and control experiments were performed to gain better insight into the reaction mechanism. peerReviewed

Selective derivatisations of resorcarenes - 2. Multiple regioselective ring closure reactions

Abstract The condensation of the C-pentyl resorcarene 1 with long chain aliphatic diamines 3a-d and excess formaldehyde leads under high dilution conditions to tetrabenzoxazine derivatives 4a-d in which pairs of adjacent oxazine rings are connected by an aliphatic chain. Six new rings are formed per resorcarene molecule during this reaction in a regioselective way. For one example (4a) the chiral cleft-like structure with C2 symmetry was proved by single crystal X-ray analysis. Hydrolysis of the oxazine rings gives the secondary amine derivatives 5a,b with C2v symmetry in high yield.

Synthesis of 7-Pentafluorophenyl-1H-indole: An Anion Receptor for Anion–π Interactions

7-Pentafluorophenyl-1H-indole has the potential to be a key compound for the investigation of anion–π interactions in solution. Unfortunately, it was not possible to obtain it by aryl–aryl coupling reaction. Finally, it has been prepared by Bartoli indole synthesis. The key compound as well as analogues were submitted to preliminary studies of anion binding. Single crystals of two key receptors were obtained.

Fliegende Kapseln: massenspektrometrische Detektion von Pyrogallaren- und Resorcinaren-Hexameren

Anion template effect and the polymerization degree

Two 2D (M1 and M2) and one 1D (M3) metal‐organic frameworks (MOFs) have been prepared from pyridine functionalized tetradentate ligand tetrakis(nicotinoxymethyl)methane TNM with silver tetrafluoroborate, nickel chloride, and copper hexafluorophosphate. M1 manifests a previously unpresented mode of 4,4 threefold parallel interpenetration for 2D MOFs. Large channels (vdW diameter 9.4 Å) through eclipsed 2D layers of M2 were observed. While the open space percentage in the noninterpenetrated M2 was 38.0 %, the triple interpenetration of the sheets of M1 reduced the void to 10.8 %. With the same ligand and a similar, weakly coordinating anion as that in M1, the structure M3 was rendered one‐dim…

Structural and metallo selectivity in the assembly of [2 × 2] grid-type metallosupramolecular species: Mechanisms and kinetic control

An unsymmetrical bis(tridentate) ligand LH in which one binding site can be readily deprotonated forms a kinetically inert [Co(III)L(2)](+) complex which can be used as a "corner" species for the "Coupe du Roi" assembly of trans,trans-[Co(2)M(2)L(4)](6+) metallogrids (M = Fe(II), Co(II), Cu(II), Zn(II)). In the mixed Co(III)/Co(II) species, the oxidation states appear to be localised. In solution, the ligand LH forms octacationic, homometallic [2 × 2] grids with the individual labile metal ions Fe(II), Co(II), Cu(II), Zn(II), seemingly as mixtures of all possible isomers arising from the unsymmetrical nature of the ligand. In the solid state, however, [Zn(4)L(4)](CF(3)SO(3))(8)·4CH(3)CN cry…

Anion modulated structural variations in copper(II) complexes with a semicarbazone Schiff base: Synthesis, characterization and self assembly

Abstract Two copper(II) complexes, [Cu(L)N3]n (1) and [Cu(HL)2](I3)ClO4 (2), where HL = 2-pyridylaldehydesemicarbazone, have been prepared and characterized by elemental analysis, IR and UV–Vis spectroscopy and single crystal X-ray diffraction studies. Complex 1 crystallizes in monoclinic space group P21/a, whereas, complex 2 crystallizes in triclinic space group P-1. Complex 1 is a stair-like coordination polymer with square pyramidal geometry of copper(II), whereas, complex 2 is a mononuclear cationic bis-ligand complex of octahedral copper(II). Lower coordination ability of tri-iodide or perchlorate compared to azide may be related with variations of the structures of the complexes.

Ion mobility-mass spectrometry of supramolecular complexes and assemblies

Despite their structural and functional differences, synthetic supramolecular assemblies share many similarities with biological assemblies, especially enzymes. The assemblies can be on the same length scale, and their structures and guest binding are typically governed by non-covalent interactions. Thus, only relatively weak interactions define the shape of a synthetic supramolecule or the secondary and tertiary structure of a protein, such that the resulting dynamism makes structure elucidation challenging. For biomolecules such as peptides, proteins, glycans and lipids this has often been tackled using ion mobility–mass spectrometry (IM-MS), whereby analyte ions are separated according t…

Divergent route to the preparation of hybrid Pt–Fe 2,4,6-Tris(4-ethynyl)phenyl-1,3,5-triazine metallodendrimers for nonlinear optics

Abstract: The synthesis strategy for the preparation of novel platinum acetylide homometallic and heterobimetallic dendrimers (containing Fe as the other metal fragment) based on a 2,4,6-tris(4-ethynyl)phenyl-1,3,5-triazine core (3) is reported. All the dendrimer generations (G0G2) were synthesized under copper-free conditions following a divergent route. The G0-Pt dendrimer (4) was synthesized using the 1,3,5-triazine core (3) and cis-[Pt(PEt3)2Cl2] with a molar ratio of 1/4. The advantage of the current method is that different dendrimers can be prepared by following the same procedure with only changes in the molar ratios of the reactants involved. For instance, when 3 reacts with 4 in a…

Two-Level Self-Organisation of Arrays of [2×2] Grid-Type Tetranuclear Metal Complexes by Hydrogen Bonding

Here we report on the synthesis and characterisation of four new complexes of the [2×2] M4II grid-type (M = Co, Fe, Zn) with oligopyridine-derived ligands. The presence of aminopyrazine and aminopyrimidine moieties at the edge of the ligands potentially enables the formation of infinite hydrogen-bonded multi-grid networks. The ligands were synthesised by subsequent stannylations and Stille-type coupling reactions. The complexes were obtained by self-assembly of the ligand with the metal salt. The single-crystal X-ray structure was determined for the Co complex 7 containing aminopyrimidine as the hydrogen-bonding moiety [P1¯; a = 15.4976(4), b = 18.2114(6), c = 31.9538(10) A, α = 86.9809(13)…

Connecting Electron-Deficient and Electron-Rich Aromatics to Support Intermolecular Interactions in Crystals

Five compounds bearing electron-deficient pentafluorophenyl as well as electron-rich (salicylate or indole) aromatic moieties connected by amide or ester linkages were investigated by X-ray diffraction. In the crystals, various interactions (π–π, lone pair–π) between the different aromatic units are important structure controlling factors in addition to the stronger inter- or intramolecular hydrogen bonds induced by the amide and ester moieties. The hydrogen bonding leads to polymeric and macrocyclic assembly of the molecular building blocks.

Synthesis and structural characterization of new transition metal complexes of a highly luminescent amino-terpyridine ligand

Abstract The synthesis, NMR and UV–Vis spectroscopy measurements and X-ray diffraction analysis of four new metal complexes of the amino terpyridine ligand 4′-[4-(4-aminophenyl)phenyl]-2,2′:6′,2″-terpyridine L, namely [FeL2](ClO4)2 (1), [ZnL2](ClO4)2 (2), [CdL2](ClO4)2 (3) and [PtMe3IL] (4), are reported. The X-ray crystal structures of complexes 1–3 are 1:2 metal:ligand structures with tridentate ligands decorated around the octahedral metal centers. In complex 4, with L in a bidentate coordination mode, the Pt(IV) coordinated methyl and iodine groups form a fac-arrangement. The 1H NMR spectrum of 4 shows three 195Pt-1H resonances for the methyl groups incorporating the fac-arrangement, wh…

Unusual interaction extended between the pyranose ring oxygen and Zn(II) center in the complexes derived from 4,6-O-butylidene/ethylidene-N-(α-hydroxynaphthylidene/o-hydroxybenzylidene)-β-d-glucopyranosylamine: Evidence for a pseudo-bicapped tetrahedral complex of Zn(II) based on the crystal structure

The Zn(II) complexes of 4,6-O-butylidene/ethylidene-N-(α-hydroxynaphthylidene/o-hydroxybenzylidene)-β-Image -glucopyranosylamine have been synthesized and characterized using spectral and analytical methods and structure for one of the products was established. The geometry of the complexes vary from unusual distorted trigonal bipyramidal to pseudo-bicapped tetrahedron depending upon the extent of binding of pyranose ring oxygens to the Zn(II) ion, as evidenced from crystal structures. Such interaction is also reflected on the optical rotation and CD spectral properties of these complexes in solution.

Hyper-CEST NMR of metal organic polyhedral cages reveals hidden diastereomers with diverse guest exchange kinetics.

AbstractGuest capture and release are important properties of self-assembling nanostructures. Over time, a significant fraction of guests might engage in short-lived states with different symmetry and stereoselectivity and transit frequently between multiple environments, thereby escaping common spectroscopy techniques. Here, we investigate the cavity of an iron-based metal organic polyhedron (Fe-MOP) using spin-hyperpolarized 129Xe Chemical Exchange Saturation Transfer (hyper-CEST) NMR. We report strong signals unknown from previous studies that persist under different perturbations. On-the-fly delivery of hyperpolarized gas yields CEST signatures that reflect different Xe exchange kinetic…

Enantiomerenreine [M6L12]- oder [M12L24]-Polyeder aus flexiblen Bis(pyridin)-Liganden

Oxoanion binding to a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties

A macrocyclic pseudopeptide 3 is described featuring three amide groups and three 1,4-disubstituted 1,2,3-triazole units along the ring. This pseudopeptide was designed such that the amide NH groups and the triazole CH groups converge toward the cavity, thus creating an environment well suited for anion recognition. Conformational studies in solution combined with X-ray crystallography confirmed this preorganisation. Solubility of 3 restricted binding studies to organic media such as 5 vol% DMSO/acetone or DMSO/water mixtures with a water content up to 5 vol%. These binding studies demonstrated that 3 binds to a variety of inorganic anions in DMSO/acetone including chloride, nitrate, sulfat…

cis-[Bis(diphenylphosphino)ethane-κ2P,P′]dichlororuthenium(II) dichloromethane disolvate

The title compound, cis-[RuCl2(C26H24P2)2]·2CH2Cl2, was obtained as an unexpected product from our attempts to prepare new ruthenium molecular wires using organic bridging ligands. Three solvates and a solvent-free structure of the isomeric complex with the chloride anions in a trans geometry have already been reported, while the cis isomer has been described only in solution studies prior to this work.

Ruthenium Metallodendrimers Based on Nitrile‐Functionalized Poly(alkylidene imine)s

The preparation of the first- and second-generation of nitrile-functionalized poly(alkylidene imine) dendrimers with the organometallic ruthenium complex [Ru(η5-C5H5)(PPh3)2Cl] peripherally attached is described. The reaction of N,N′-bis(cyanomethyl)piperazine (1), N,N′-bis[N′′,N′′′-bis(cyanoethyl)aminoethyl]piperazine (2), or N,N,N′,N′-tetrakis(cyanoethyl)ethylenediamine (3) with [Ru(η5-C5H5)(PPh3)2Cl] (4) in the presence of TlPF6 gives the new air-stable ruthenium metallodendrimers 5, 6, and 7, respectively. These stable metallodendrimers are easily prepared and represent a novel quantitative method to solidify and chromatographically purify the otherwise semi-liquid nitrile-functionalize…

Nano-sized I12L6 Molecular Capsules Based on the [N⋅⋅⋅I+⋅⋅⋅N] Halogen Bond

Summary Self-assembly of pre-organized subunits with a concave overall shape is an effective strategy for the synthesis of supramolecular capsules. We report the synthesis of a cavitand-based hexameric capsule held together solely by 12 robust [N⋅⋅⋅I + ⋅⋅⋅N] halogen bonds and its characterization in solution and in the gas phase via 1 H NMR spectroscopy, diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY), and electrospray ionization mass spectrometry. The [N⋅⋅⋅I + ⋅⋅⋅N] halogen-bonded hexameric capsule was efficiently synthesized from the isolobal metallosupramolecular Ag + capsule by application of the [N⋅⋅⋅Ag + ⋅⋅⋅N] → [N⋅⋅⋅I + ⋅⋅⋅N] cation-exchange reaction.

Gas-phase H/D-exchange reactions on resorcinarene and pyrogallarene capsules: Proton transport through a one-dimensional Grotthuss mechanism

Hydrogen/deuterium exchange (HDX) experiments can be used to examine the gas-phase structure of hydrogen-bonded dimeric resorcinarene and pyrogallarene capsules. Already the qualitative comparison of the isotope exchange rates of different host–guest complexes with Cs+, tetramethyl ammonium (TMA+) and tetraethyl ammonium (TEA+) as the guest cations provides insight into the H/D-exchange mechanisms and with it, into the capsules' gas-phase ion structures. The smaller Cs+cations bind inside dimeric capsules with an intact seam of hydrogen bonds between the two monomers. Larger cations such as TEA+ lead to capsules with partially disrupted seams of hydrogen bonds. A fast isotope exchange is on…

Binding motif of ebselen in solution: Chalcogen and hydrogen bonds team up

Ebselen (2-phenyl-1,2-benzoselenazol-3(2H)one), a glutathione peroxidase mimic, is active against several RNA viruses, among others the retrovirus responsible for the COVID-19 pandemic. In this paper 77Se and 1H NMR studies of ebselen are reported and they identify the chalcogen bond (ChB) and hydrogen bond (HB) that are central in the landscape of interactions formed by the compound in solution. The selenium atom and the hydrogen atom at the C7 carbon act as ChB and HB donors and the O and N atoms of neutral molecules function as acceptors. The ChB and HB give rise to a bifurcated supramolecular synthon, which fastens the interaction acceptor opposite to the N–Se covalent bond of the selen…

One-step synthesis of resorcarene dimers composed of two tetra-benzoxazine units

Abstract The condensation of resorcarene 1 with ethylenediamine and an excess of formaldehyde gives, under high dilution conditions, in up to 15% yield the octa-benzoxazine dimer 2 in which two molecules of 1 are connected by four bridges. The structure of 2 has been confirmed by 1 H NMR spectra and MALDI-TOF mass spectra and by hydrolysis of the oxazine rings yielding the secondary amine 3 .

Steroidal supramolecular metallogels

The review deals with an expanding number of steroidal compounds that are capable of forming a metallogel providing a multitude of novel materials rich in their properties. The future of steroidal metallogels holds a myriad of potential applications as new intelligent materials. Detection of potentially harmful compounds without expensive instrumentation, entrapment of environmentally hazardous substances, and sensitive and selective nanomaterials represent only a few of these potential applications. This article reviews the design, synthesis, characterization, and applications of steroidal metallogels. peerReviewed

Diastereoselective formation of highly functionalised α-substituted amino acid derivatives via aldol addition

Abstract Highly diastereoselective aldol additions of (2 R ,4 S )-3- tert -butyl 4-methyl 2- tert -butyloxazolidine-3,4-dicarboxylate ( 1 ) are reported. The utility of the highly substituted oxazolidines of type 1 for diastereoselective α-addition of the fully protected amino acid l -serine with achiral and chiral carbonyl compounds is demonstrated and the relative and absolute configuration of the aldol products are discussed on the basis of NOESY data and solid state structures of selected examples. The aldol products represent highly useful intermediates in the syntheses of sphingosine-related metabolites.

Asymmetric [N–I–N]+ halonium complexes

The first asymmetric halogen-bonded iodonium complexes [I(py)(4-DMAP)]PF6 (2c) and [I(py)(4-Etpy)]PF6 (2e) were prepared via [N–Ag–N]+ → [N–I–N]+ cation exchange of their analogous 2-coordinate silver complexes. The complexes were characterised by 1H and 1H–15N HMBC NMR spectroscopy, and single crystal X-ray crystallography.

Syntheses and characterization of novel ruthenium complexes based on 1,3-dicyanobenzene

Submitted by António Freitas (amsf@uma.pt) on 2019-06-14T13:25:52Z No. of bitstreams: 1 Syntheses and Characterization of Novel Ruthenium Complexes Based on 13-DicyanobenzeneJoãoRodrigues.pdf: 354444 bytes, checksum: edc8aaaa84900d75321648e76e0c8e27 (MD5) Made available in DSpace on 2019-06-14T13:25:52Z (GMT). No. of bitstreams: 1 Syntheses and Characterization of Novel Ruthenium Complexes Based on 13-DicyanobenzeneJoãoRodrigues.pdf: 354444 bytes, checksum: edc8aaaa84900d75321648e76e0c8e27 (MD5) Previous issue date: 2007 info:eu-repo/semantics/publishedVersion

Entrapment of a linear water pentamer into a uranyl-salophen dimer in the solid state

In the solid state, uranyl-salophen complex 1, decorated with bipyridyl sidearms, self-assembles from moist acetonitrile into dimeric species displaying a confined water pentamer, as observed by X-ray diffraction on single crystals. The linear water cluster is incarcerated within the dimeric cavity by coordination to the Lewis acidic uranyl centres and by a network of hydrogen bonds established with the pyridinic nitrogen atoms on the sidearms.

The conversion from cellulose I to cellulose II in NaOH mercerization performed in alcohol–water systems: An X-ray powder diffraction study

Abstract The slurry-mercerization (SM) processes in 2-propanol–water and 2-propanol–ethanol–water and wet-mass-mercerization (WMM) process in ethanol–water solvents are investigated. Based on X-ray diffraction measurements in the earlier reports, we have derived a mathematical method to evaluate more exactly the conversion of cellulose I (CI) to cellulose II (CII) and used it to survey the effects of different alkali treatments on cellulose crystals. This method is very useful when the crystal system changes in a certain set of experiments are compared with each other. The optimal alcohol concentration in SM processes was found to be 80–92 w/w-% in 2-propanol–water solution, 85–90 w/w-% in …

Capturing Hydrophobic Trifluoroiodomethane in Water into an M 4 L 6 Cage

Synthetically important trifluoroiodomethane (CF3I) was trapped in water by using a metal–organic supramolecular anionic cage. Under ambient conditions, nearly 1:1 encapsulation of the hydrophobic, gaseous CF3I substrate with the cage was observed, and its binding constant was calculated by relative comparison with benzene encapsulation.

Novel γ-turn mimetics with a reinforced hydrogen bond

Abstract Pyridylmethylphenols 2 can mimic the geometry of γ-turns. Hydrogen bonding in 2 has been characterized by X-ray crystallography, IR and NMR spectroscopy, and molecular modeling.

Complexation of Small Molecules by Open-Ended Resorcarene Hosts

[structure: see text] Sterically hindered tetraaminomethylated resorcarenes form inclusion complexes in CDCl(3) with acetonitrile and acetaldehyde, which are kinetically stable on the NMR time scale at 233 K.

Retraction notice to “trans-Tetrakis(pyridine)dichloroiron(II) as catalyst for Suzuki cross-coupling in ethanol and water” [Tetrahedron Lett. 49 (2008) 6679]

Chemistry with Roataxanes: Intra- and Intermolecularly Covalently Linked Rotaxanes

The direct introduction of sulfonamide units (cf. 9) into carboxamide-based rotaxanes allows us to intramolecularly bridge the “wheel” and the “axle” of such species for the first time as is shown by the bridged bissulfonamide rotaxane 11. Due to its stronger acidity the SO2-NH proton can be selectively abstracted by mild bases even in the presence of CO.NH and then be substituted by treatment with suitable iodo compounds. This leads intramolecularly to 11 (71% yield) and intermolecularly to bis[2]rotaxane 16 (76% yield). The iodo-substituted rotaxane 15 isolated as a remarkably stable byproduct offers a new synthetic potential demonstrated by the preparation of 16.

Tridentate C–I⋯O−–N+ halogen bonds

The X-ray structures of the first co-crystals where the three oxygen lone pairs in N-oxides are fully utilized for tridentate C–I⋯O−–N+ halogen bonding with 1,ω-diiodoperfluoroalkanes are reported, studied computationally, and compared with the corresponding silver(I) N-oxide complexes.

Two-photon absorption of BF2-carrying compounds: insights from theory and experiment

This communication presents a structure–property study of a few novel pyridine-based difluoroborate compounds with a N–BF2–O core, which exhibit outstanding fluorescence properties. To exploit their potential for two-photon bioimaging, relationships between the two-photon action cross section and systematic structural modifications have been investigated and unravelled.

Ion-Pair Recognition of Tetramethylammonium Salts by Halogenated Resorcinarenes

The non-covalent interactions of different upper-rim-substituted C(2)-resorcinarenes with tetramethylammonium salts were analyzed in the gas phase in an Electrospray Ionization Fourier-transform ion-cyclotron-resonance (ESI-FTICR) mass spectrometer and by (1)H NMR titrations. The order of binding strengths of the hosts towards the tetramethylammonium cation in the gas phase reflects the electronic nature of the substituents on the upper rim of the resorcinarene. In solution, however, a different trend with particularly high binding constants for halogenated resorcinarenes has been observed. This trend can be explained by a synergetic effect originating from the interaction of the halogenate…

Self-assembly of a M4L6 complex with unexpected S4 symmetry

Using 1,4-diaminobenzene and 2-formylpyridine as simple building blocks results in a 1D ligand (rod, L2) to 2D (M4L4 grid, C1) to 3D (S4 symmetrical M4L6, C2) complexes upon sequential addition of Cu(I) and Fe(II) ions. The complex C2 can be seen as the smallest possible pseudo-tetrahedron with S4 symmetry. peerReviewed

Naphthalene Derivatives from the Roots of Pentas parvifolia and Pentas bussei

The phytochemical investigation of the CH2Cl2/MeOH (1:1) extract of the roots of Pentas parvifolia led to the isolation of three new naphthalenes, parvinaphthols A (1), B (2), and C (3), two known anthraquinones, and five known naphthalene derivatives. Similar investigation of the roots of Pentas bussei afforded a new polycyclic naphthalene, busseihydroquinone E (4), a new 2,2'-binaphthralenyl-1,1'-dione, busseihydroquinone F (5), and five known naphthalenes. All purified metabolites were characterized by NMR and MS data analyses, whereas the absolute configurations of 3 and 4 were determined by single-crystal X-ray diffraction studies. The E-geometry of compound 5 was supported by DFT-base…

Dimeric resorcinarene salt capsules with very tight encapsulation of anions and guest molecules

Crystallization of N-cyclohexyl ammonium resorcinarene triflate from methanol results in a dimeric capsule capable of trapping two triflate anions and two methanol molecules within a 341 A3 cavity while with 1,4-dioxane as a guest it forms a new larger dimeric capsule with volume of 679 A3 encapsulating four 1,4-dioxane and four water molecules, resulting in packing coefficients of 0.75 and 0.67, respectively.

Enantiomerically pure [M(6)L(12)] or [M(12)L(24)] polyhedra from flexible bis(pyridine) ligands.

Coordination-driven self-assembly is one of the most powerful strategies to prepare nanometer-sized discrete (supra)molecular assemblies. Herein, we report on the use of two constitutionally isomeric BINOL-based bis(pyridine) ligands for this purpose. Upon coordination to Pd(II) ions these self-assemble into enantiomerically pure endo- and exo-functionalized hexa- and dodecanuclear metallosupramolecular spheres with a chiral skeleton depending on the substitution pattern of the BINOL core. These aggregates were characterized by NMR, MS, DLS, TEM, and EELS as well as ECD. Furthermore, experimental ECD data could be compared to those obtained from theoretical simulations using a simplified Ta…

Isoflavones and Rotenoids from the Leaves of Millettia oblata ssp. teitensis

A new isoflavone, 8-prenylmilldrone (1), and four new rotenoids, oblarotenoids A−D (2−5), along with nine known compounds (6−14), were isolated from the CH2Cl2/CH3OH (1:1) extract of the leaves of Millettia oblata ssp. teitensis by chromatographic separation. The purified compounds were identified by NMR spectroscopic and mass spectrometric analyses, whereas the absolute configurations of the rotenoids were established on the basis of chiroptical data and in some cases by single-crystal X-ray crystallography. Maximaisoflavone J (11) and oblarotenoid C (4) showed weak activity against the human breast cancer cell line MDA-MB-231 with IC50 values of 33.3 and 93.8 μM, respectively. peerReviewed

ChemInform Abstract: Structural Macrocyclic Supramolecular Chemistry

Asymmetric synthesis of functionalized tetrahydrofluorenones via an NHC-catalyzed homoenolate Michael addition

The first example of an N-heterocyclic carbene-catalyzed asymmetric desymmetrization of enal-tethered cyclohexadienones via an intramolecular homoenolate Michael addition/esterification reaction is described. This new protocol offers a direct entry to various functionalized tetrahydrofluorenones with three contiguous stereocenters in high yields, good diastereoselectivities and excellent enantioselectivities.

Solid state anion–π interactions involving polyhalides

The stabilization of polyhalides in the solid state with the support of electron-deficient pentafluorophenyl groups is described. Furthermore, a synthetic approach towards the sensitive tetraiodide dianion is described and ESI mass spectrometric evidence for its presence in solution is reported.

Asymmetric synthesis of 3,3′-pyrrolidinyl-dispirooxindoles via a one-pot organocatalytic Mannich/deprotection/aza-Michael sequence

Chemical communications 52, 2249-2252 (2016). doi:10.1039/C5CC10057G

trans-Bis[bis(diphenylphosphino)methane-κ2P,P′]dichlororuthenium(II) dichloromethane disolvate acetone hemisolvate hemihydrate

Submitted by António Freitas (amsf@uma.pt) on 2019-06-14T10:31:02Z No. of bitstreams: 1 trans-Bis[bis(diphenylphosphino)methane-j2P,P000]dichlororuthenium(II) dichloromethane disolvate acetone hemisolvate hemihydrate.pdf: 221219 bytes, checksum: 8e4738b39248ecff6cd2421345c563e7 (MD5) Made available in DSpace on 2019-06-14T10:31:02Z (GMT). No. of bitstreams: 1 trans-Bis[bis(diphenylphosphino)methane-j2P,P000]dichlororuthenium(II) dichloromethane disolvate acetone hemisolvate hemihydrate.pdf: 221219 bytes, checksum: 8e4738b39248ecff6cd2421345c563e7 (MD5) Previous issue date: 2006 info:eu-repo/semantics/publishedVersion

Bis (μ-tetrazolato-NN′) bridged dinuclear nickel(II) Schiff base complexes: Tandem synthesis, structure and self assembly

Abstract Two new bis(μ-tetrazolato-NN′) bridged dinuclear nickel(II) Schiff base complexes [Ni2L12(PTZ)2]·2(CH3)2SO·2.69H2O (1) and 2[Ni2L22(PTZ)2]·3H2O (2) (HL1 and HL2 are Schiff bases, HL1 = 2-((2-(dimethylamino)ethylimino)methyl)phenol, HL2 = 2-((2-(methylamino)ethylimino)methyl)-6-methoxyphenol and HPTZ is 5-pyrazinyltetrazole) have been synthesized via [3+2] cyclo-addition of 2-cyanopyrazine and sodium azide in presence of nickel(II) acetate tetrahydrate and the respective Schiff bases. The structures of the complexes are confirmed by single crystal X-ray diffraction analysis. Both complexes show fluorescence. The change in the denticity of the Schiff base blocking ligand is shown to …

Guest-Induced Folding of the N-Benzyl Substituents in an Ammonium Resorcinarene Chloride and the Formation of a Halogen-Bonded Dimer of Capsules

In methanol, N-benzyl ammonium resorcinarene chloride (Bn-NARCl) crystallizes as a solvate with the benzyl groups oriented in an open flower-like manner parallel to the cation–anion seam. 1,4-Dioxane as guest triggers a “semi-closed” single-molecule capsule with two benzyl “arms” enclosing the guest. The introduction of halogen bond (XB) donor 1,4-diiodoperfluorobutane (1,4-DIOFB) additionally folds the remaining two benzyl arms thus resulting in a fully closed capsule. Two 1,4-DIOFB molecules bridge two such Bn-NARCl capsules, forming a 2:2:2 XB held dimeric assembly of single-molecule capsules. The peculiar behavior was not observed in the bromide analog under similar experimental conditi…

First Chemosensor for Selective Detection and Quantification of L-4-Hydroxyproline in Collagen and Other Bio Samples.

Amino pyridine-based rhodamine conjugate (APR) has been developed as a first chemosensor for selective detection and quantification of L-4-Hydroxyproline (Hyp). The “turn-on” fluorescence property of the chemosensor makes it unique for easy estimation of Hyp in collagen and biological samples. peerReviewed

Structural Studies of Self-Folding Cavitands

Metal-bound Nitrate Anion as an Acceptor for Halogen Bonds in mono-Halopyridine-Copper(II) nitrate Complexes

Fifteen n-halopyridine-Cu(NO3)2 complexes (n = 2, 3, 4) obtained from two different solvents, acetonitrile and ethanol, are investigated for C–X···O–N halogen bonds (XBs) in the solid state by single and powder X-ray diffraction. The nitrate anions bind copper(II) via anisobidentate modes and one of three oxygens act as an XB acceptor to halogens on the core pyridine rings. The N-metal coordination activates the electron-deficient π-system and triggers even C2- and C4-chlorines in the corresponding [Cu(2-chloropyridine)2(NO3)2] and [Cu(4-chloropyridine)2(NO3)2(ACN)] complexes to form short C–Cl2/Cl4···O–N halogen bonds. Notably, the C2–Cl2···O–N XBs with a normalized XB distance parameter (…

Self‐Assembly and Characterisation of Grid‐Type Iron( II ), Cobalt( II ) and Zinc( II ) Complexes

The reaction of the ligands 5 and 6, containing two tridentate binding units, with iron(II), cobalt(II) and zinc(II) leads to the self-assembly of supramolecular architectures of [2 × 2] grid type containing four ions in octahedral coordination sites. The grid-type structures have been assigned on the basis of the spectroscopic data in solution, and confirmed in the solid state in the case of complexes 6b and 6c by X-ray crystallography. The latter study revealed that each metal ion is situated in a distorted octahedral coordination environment comprising two N,N,O ligand donor sets. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

Selective Recognition of Phenazine by 2,6‐Dibutoxylnaphthalene‐Based Tetralactam Macrocycle

A 2,6‐dibutoxylnaphthalene‐based tetralactam macrocycle was designed and synthesized. This macrocycle shows highly selective recognition to phenazine ‐‐ a well‐known secondary metabolite in bacteria and an emerging disinfection byproduct in drinking water. In contrast, the macrocycle shows no binding to the structurally similar dibenzo‐1,4‐dioxin. It was revealed that hydrogen bonding, π‐π and σ‐π interactions are the major driving forces between phenazine and the new tetralactam macrocycle. A perfect complementarity in electrostatic potential surfaces may explain the high selectivity. In addition, the macrocycle shows fluorescent response to phenazine, demonstrating its potential in fluore…

Halogen bonded supramolecular complexes and networks

In spite of some controversy of the true nature of the interaction between polarized halogen atoms and neutral or charged Lewis bases, termed “halogen bonding”, as a primary interaction, it is a very useful new tool/way to construct supramolecular complexes and networks. This is especially true in solid state supramolecular chemistry where utilization of weak intermolecular interactions such as halogen bonding opens up new insights to materials design and supramolecular synthesis.

Retracted Article: Differential detection and quantification of cyclic AMP and other adenosine phosphates in live cells

A new naphthol-based rhodamine derivative (NpRD) has been developed for the selective and differential detection of adenosine 3′,5′-cyclic monophosphate (cAMP) and adenosine phosphates (APs) (ATP, ADP, and AMP) from other nucleotides. The simple detection and quantification of cAMP in human blood cells and in other samples based on the ‘turn on’ fluorescence properties of this chemosensor through colorimetry or fluorometry makes it unique for probable application in high throughput screening.

Red and blue luminescent metallo-supramolecular coordination polymers assembled through π–π interactions †

The use of π-stacking interactions to control the aggregation of photo-active metal centres is explored through the design of bis(2,2′;6′,2′′-terpyridyl) metal complexes functionalised with biphenyl ‘tails’. Aryl–aryl interactions control the aggregation of the metal complexes into polymetallic arrays in the solid state. Cobalt(II), ruthenium(II), nickel(II), copper(II), zinc(II) and cadmium(II) bis-ligand complexes and a mixed ligand ruthenium(II) complex have been structurally characterised. The solid-state structures are dependent on which units dominate the π-stacking. For cobalt, ruthenium, nickel and copper, biphenylene–biphenylene interactions lead to linear rod-like arrays, while fo…

Connecting Electron-Deficient and Electron-Rich Aromatics to Support Intermolecular Interactions in Crystals (Eur. J. Org. Chem. 15/2015)

Synthesis of vinca alkaloids and related compounds LX. A simple transformation of apovincamine into vincamine

Abstract The 15α-chloro-vincamine derivative 2 was prepared and proved to be key intermediate of a two-step transformation of apovincamine into vincamine. The structure of 2 was established via detailed NMR and X-ray investigations.

Halogen-bonded capsules

Enantiomeric Resolution of Asymmetric-Carbon-Free Binuclear Double-Stranded Cobalt(III) Helicates and Their Application as Catalysts in Asymmetric Reactions

A series of double-stranded binuclear helicates [Co2(H1)2]4+, [Co2(H2)2]4+, and [Co2(H3)2]4+, derived from monodeprotonated bis-pyridyl hydrazine-based ligands of H21, H22, and H23 with one, two, and three -CH2 spacers, were obtained. These asymmetric-carbon-free racemic helicates were separated into their ΔΔ and ΛΛ enantiomers. The resolved helicates were examined for the first time as enantioselective catalysts in asymmetric benzoylation and nitroaldol reactions.

Do 2-coordinate iodine(I) and silver(I) complexes form Nucleophilic Iodonium Interactions (NIIs) in solution?

The interaction of a [bis(pyridine)iodine(I)]+ cation with a [bis(pyridine)silver(I)]+ cation, in which an iodonium ion acts as nucleophile by transferring electron density to the silver(I) cation, is reinvestigated herein. No measurable interaction is observed between the cationic species in solution by NMR; DFT reveals that if there is an attractive interaction between this complexes in solution, it is dominantly the π-π interaction of pyridines peerReviewed

Size- and Structure-Selective Noncovalent Recognition of Saccharides by Tetraethyl and Tetraphenyl Resorcinarenes in the Gas Phase

The noncovalent complexation of tetraethyl and tetraphenyl resorcinarenes with mono-, di-, and oligosaccharides was studied with negative-polarization electrospray ionization quadrupole ion trap and electrospray ionization Fourier-transform ion cyclotron resonance mass-spectrometric analysis. The saccharides formed 1:1 complexes with deprotonated resorcinarenes, which exhibited clear size and structure selectivity in their complexation. In the case of the monosaccharides, hexoses formed much more abundant and kinetically stable complexes than pentoses or deoxyhexoses. A comparison of the mono-, di-, and oligosaccharides revealed that both the relative abundance and stability of the complexe…

Selective encapsulation and enhancement of the emission properties of a luminescent Cu(I) complex in mesoporous silica

We describe a synthetic approach to prepare new luminescent silica‐based materials through the encapsulation of a neutral copper(I) complex inside the pores of mesoporous silica nanoparticles (MSN). The copper(I) complex is present, in the solid state, as two polymorphs, blue and yellow emissive, and in solution it shows a pale yellow color that is also mirrored by an emission in the yellow‐orange region of the electromagnetic spectrum. The X‐ray structures of single crystals have been obtained for both polymorphs. The complex encapsulation in MSN is achieved by its entrapment inside micelles followed by condensation of the silica source. Interestingly, the entrapment leads to the isolation…

Inside Cover: A Self-Assembled M8L6 Cubic Cage that Selectively Encapsulates Large Aromatic Guests (Angew. Chem. Int. Ed. 15/2011)

Organocatalytic Asymmetric Synthesis of 2,3′-Connected Bis-Indolinones by Mannich Reactions of N-Acetylindolin-3-ones with Isatin N-Boc Ketimines

A highly diastereo- and enantioselective Mannich reaction of N-acetylindolin-3-ones with isatin N-Boc ketimines to form 2,3′-connected bis-indolinones is developed employing a low loading of a readily available bifunctional thiourea catalyst. The asymmetric synthesis connects two indolinones via a vic-diamine unit and generates two neighboring stereocenters.

Selective gas adsorption by calixarene-based porous octahedral M32 coordination cages

Giant octahedral M32 coordination cages were prepared via self-assembly of sulfonylcalix[4]arene-supported tetranuclear M(II) clusters (M = Co, Ni) with hybrid linker based on tris(dipyrrinato)cobalt(III) complexes appended with peripherical carboxylic groups. Due to intrinsic and extrinsic porosity, the obtained solid-state supramolecular architectures demonstrated good performance as adsorbents for the separation of industrially important gases mixtures. peerReviewed

X-Ray and NMR Studies on Host-Guest Inclusion Complex Formation between Crown Ethers and Pyridinium Compounds

Aromatic–aromatic, π–π, and cation–π interactions can be exploited in the preparation of molecular complexes between benzene-substituted crown ethers and pyridium cations. These complexes have been studied in the gas phase, in solution, and in the solid state; the structure of one of the complexes is depicted on the right.

Synthesis and Structure of Trimethylplatinum(IV) Iodide Complex of 4'-(4-Methoxyphenyl)-2,2':6',2''-terpyridine Ligand and its Halogen Bonding Property

Copper(II) complexes of 3-aminopropanols. Synthesis and structure of (3-aminopropanolato)formatocopper(II)

Abstract The crystal and molecular structure of the title compound has been determined from single-crystal X-ray data and refined to a final R value of 0.030 for 971 reflections. The compound crystallizes in the monoclinic space group P21/c with two dimeric molecules in a cell of dimensions a=856.9(1), b= 887.7(1), c=837.0(1) pm and β=99.55(1)°. The blue crystals of Cu(ap)(HCOO) (ap=3-aminopropanolato ion) are made of centrosymmetric dialkoxy bridged dimers (Cu…Cu 296.4(1) pm). The dimers are polymerized along the c axis into chains via two NHO hydrogen bonds (Cu…Cu 547.9(1) pm). These chains are joined together along the b axis by CuOCOCu bridges and NHO hydrogen bonds (Cu…Cu 462.2(1) pm…

Recognition of alkali metal halide contact ion pairs by uranyl-salophen receptors bearing aromatic sidearms. The role of cation-pi interactions.

Hard anions have long been known to bind strongly to the uranium of uranyl-salophen complexes. Upon functionalization of the salophen framework with one or two benzyloxy substituents, efficient ditopic receptors for alkali metal ions are obtained. The solid-state structures of complexes formed by the two-armed receptor 1 with CsF and with the chlorides of K+, Rb+, and Cs+ reported here reveal the existence of dimeric supramolecular assemblies in which two receptor units assemble into capsules fully enclosing (MX)2 ion quartets. In addition to the strong coordinative binding of the anion to the uranyl center and to electrostatic cation-anion interactions, stabilizing interactions arise from …

Rigid biobased polycarbonates with good processability based on a spirocyclic diol derived from citric acid

Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bicyclic diketone (cis-bicyclo[3.3.0]octane-3,7-dione, obtained from citric acid) using trimethylolpropane. This spiro-diol monomer has two reactive primary hydroxyl groups and the synthesis from inexpensive biobased starting materials is straightforward and readily upscalable, involving no chromatographic purification. In order to explore the useful…

Superchiral Pd 3 L 6 Coordination Complex and Its Reversible Structural Conversion into Pd 3 L 3 Cl 6 Metallocycles

Large, non-symmetrical, inherently chiral bispyridyl ligand L derived from natural ursodeoxycholic bile acid was used for square-planar coordination of tetravalent Pd(II) , yielding the cationic single enantiomer of superchiral coordination complex 1 Pd3 L6 containing 60 well-defined chiral centers in its flower-like structure. Complex 1 can readily be transformed by addition of chloride into a smaller enantiomerically pure cyclic trimer 2 Pd3 L3 Cl6 containing 30 chiral centers. This transformation is reversible and can be restored by the addition of silver cations. Furthermore, a mixture of two constitutional isomers of trimer, 2 and 2', and dimer, 3 and 3', can be obtained directly from …

Synthesis and Characterisation of Chiral Triazole-Based Halogen-Bond Donors: Halogen Bonds in the Solid State and in Solution

A general platform for the synthesis of various chiral halogen-bond (XB) donors based on the triazole core and the characterisation of factors that influence the strength of the halogen bond in the solid state and in solution are reported. The characterisation of XB donors in the solid state by X-ray crystallography and in solution by 1H NMR titration can be used to aid the design of new XB donors. We describe the first example of a XB between iodotriazoles and thioureas in solution. In addition, the enantiodiscrimination of acceptors in solution through halogen-bond participation is described.

4,4'-[Thiophene-2,5-diylbis(ethyne-2,1-diyl)]dibenzonitrile

In the solid state, the title compound, C(22)H(10)N(2)S, forms centrosymmetric dimers by pairs of non-classical C-H⋯S hydrogen bonds linking approximately coplanar mol-ecules. The benzene ring involved in this inter-action makes a dihedral angle of only 7.21 (16)° with the thio-phene ring, while the other benzene ring is twisted somewhat out of the plane, with a dihedral angle of 39.58 (9)°. The hydrogen-bonded dimers stack on top of each other with an inter-planar spacing of 3.44 Å. C-H⋯N hydrogen bonds link together stacks that run in approximately perpendicular directions. Each mol-ecule thus inter-acts with 12 adjacent mol-ecules, five of them approaching closer than the sum of the van …

Solvent induced single-crystal to single-crystal structural transformation and concomitant transmetalation in a 3D cationic Zn(II)-framework.

A 3D cationic Zn(II) framework, based on Zn2(CO2)4 paddle-wheel secondary building units (SBUs) and Zn16(CO2)32 polyhedral supramolecular building blocks (SBBs), has been synthesized. At room temperature, the framework undergoes guest solvent triggered reversible structural transformation and concomitant Zn(II) to Cu(II) transmetalation in a single-crystal to single-crystal fashion.

Structural Versatility of Anion−π Interactions in Halide Salts with Pentafluorophenyl Substituted Cations

A series of pentafluorophenyl substituted ammonium, iminium, amidinium, and phosphonium halides are presented which show extensive anion-pi interactions. Hereby, the well-known anion-donor-pi-acceptor as well as "eta6" anion-pi-complex type interactions are observed. The latter is supported by fixation of the anion on top of the aromatic system through hydrogen bonding. This arrangement was investigated by theoretical methods showing a highly attractive anion-pi interaction. In addition an eta2-type coordination of the anions to only two C-atoms of the electron-deficient ring system is described.

The complexation of tetraphenylborate with organic N-heteroaromatic cations

Complexation studies of eleven N-heteroaromatic cations with tetraphenylborate are reported. Tetraphenylborate forms complexes with five cations and reacts to form Lewis-base boranes with six cations. The complexes and the displacement reaction products were characterised by 1H NMR spectroscopy, elemental analysis and crystallographic methods. In the complexes C–H⋯π or N–H⋯π hydrogen bonds are the principal intermolecular interactions. The stability constants for the complexes are determined by 1H NMR titration in acetonitrile–methanol (1 ∶ 1) solution. Crystal structures of four of the complexes and three of the Lewis-base triphenylborane products are reported.

cis-Diazido[bis(diphenylphosphino)methane-κ2P,P′]ruthenium(II) dichloromethane 0.42-solvate

Submitted by António Freitas (amsf@uma.pt) on 2019-06-13T13:44:22Z No. of bitstreams: 1 cis-Diazidobis(diphenylphosphino)methane-j2PP000ruthenium(II) dichloromethane 0.42-solvateJoãoRodrigues.pdf: 167616 bytes, checksum: 2ba0b7a76027be3eda26ce11d43fec66 (MD5) Made available in DSpace on 2019-06-13T13:44:22Z (GMT). No. of bitstreams: 1 cis-Diazidobis(diphenylphosphino)methane-j2PP000ruthenium(II) dichloromethane 0.42-solvateJoãoRodrigues.pdf: 167616 bytes, checksum: 2ba0b7a76027be3eda26ce11d43fec66 (MD5) Previous issue date: 2006 info:eu-repo/semantics/publishedVersion

Copper(II) complexes with tridentate N2O donor Schiff base isomers: Modulation of molecular and crystalline architectures through supramolecular interactions

Abstract Four copper(II) complexes, [Cu(L1)(μ-Cl)]n (1), [Cu2(L2)2(μ-Cl)2] (2), [Cu(L1)(μ1,5-NCNCN)]n (3) and [Cu(L2)(μ1,5-NCNCN)]n (4), where HL1 = 1-[(2-dimethylamino-ethylimino)-methyl]-naphthalen-2-ol and HL2 = 1-[(2-ethylamino-ethylimino)-methyl]-naphthalen-2-ol, acting as tridentate N2O donor ligands, have been prepared and characterized by elemental analysis, IR and UV–Vis spectroscopy and single crystal X-ray diffraction studies. Complexes 1, 3 and 4 show polymeric chain structures, whereas 2 has a double chloride bridged dimeric structure. The existence of C–H⋯π interactions between the dimeric units of 2 gives rise to a 2D supramolecular network. Complex 3 shows a zipper structure…

Rücktitelbild: Water Structure Recovery in Chaotropic Anion Recognition: High-Affinity Binding of Dodecaborate Clusters to γ-Cyclodextrin (Angew. Chem. 23/2015)

Selective recognition of aromatic hydrocarbons by endo-functionalized molecular tubes via C/N-H⋅⋅⋅π interactions

Molecular recognition of aromatic hydrocarbons by four endo-functionalized molecular tubes has been studied by 1H NMR spectroscopy, computational methods, and single crystal X-ray crystallography. The binding selectivity is rationalized by invoking shape complementarity and dipole alignment. The non-covalent interactions are proved to predominantly be C/N-H⋅⋅⋅π interactions. peerReviewed

Au25(SEt)18 a nearly naked thiolate-protected Au25 cluster Struct. analysis by single crystal X-ray crystallograp. and electron nuclear double res

X-ray crystallography has been fundamental in discovering fine structural features of ultrasmall gold clusters capped by thiolated ligands. For still unknown structures, however, new tools capable of providing relevant structural information are sought. We prepared a 25-gold atom nanocluster protected by the smallest ligand ever used, ethanethiol. This cluster displays the electrochemistry, mass spectrometry, and UV-vis absorption spectroscopy features of similar Au25 clusters protected by 18 thiolated ligands. The anionic and the neutral form of Au25(SEt)18 were fully characterized by (1)H and (13)C NMR spectroscopy, which confirmed the monolayer's properties and the paramagnetism of neutr…

A Halogen-Bonded Dimeric Resorcinarene Capsule.

Iodine (I2) acts as a bifunctional halogen-bond donor connecting two macrocyclic molecules of the bowl-shaped halogen-bond acceptor, N-cyclohexyl ammonium resorcinarene chloride 1, to form the dimeric capsule [(1,4-dioxane)3@1(2)(I2)2]. The dimeric capsule is constructed solely through halogen bonds and has a single cavity (V=511 Å(3)) large enough to encapsulate three 1,4-dioxane guest molecules.

Halonium ions as halogen bond donors in the solid state [xl2]y complexes

The utilization of halogen bonding interactions is one of the most rapidly developing areas of supramolecular chemistry. While the other weak non-covalent interactions and their influence on the structure and chemistry of various molecules, complexes, and materials have been investigated extensively, the understanding, utilizations, and true nature of halogen bonding are still relatively unexplored. Thus its final impact in chemistry in general and in materials science has not yet been fully established. Because of the polarized nature of a Z–X bond (Z=electron-withdrawing atom or moiety and X=halogen atom), such a moiety can act as halogen bond donor when the halogen is polarized enough by…

Synthesis, characterization and self-assembly of three dicyanamide bridged polynuclear copper(II) complexes with N2O donor tridentate Schiff bases as blocking ligands

Three copper(II) complexes [Cu(L1)(μ1,5-dca)]n (1), [Cu(L2)(μ1,5-dca)]n (2) and [Cu(L3)(μ1,5-dca)]n (3) [where HL1 = (1-(2-(dimethylamino)ethylimino)ethyl) naphthalene-1-ol, HL2 = (1-(2-(methylamino)ethylimino)ethyl) naphthalene-1-ol and HL3 = (1-(2-(ethylamino)ethylimino)ethyl)naphthalene-1-ol] have been synthesized and characterized by elemental analysis, IR and UV–Vis spectroscopy. The structure of each complex has been confirmed by single-crystal X-ray diffraction studies. In all three complexes, copper(II) centres are bridged by dicyanamide in end to end fashion. Complexes 1 and 2 are zigzag polymers, whereas complex 3 is a helical one. The weak forces like C–H⋯π and π⋯π interactions i…

Entrapment of a linear water pentamer into a uranyl-salophen dimer in the solid state

In the solid state, uranyl-salophen complex 1, decorated with bipyridyl sidearms, self-assembles from moist acetonitrile into dimeric species displaying a confined water pentamer, as observed by X-...

Simultane endo - und exo -Komplexbildung von Pyridin[4]aren-Dimeren mit neutralen und anionischen Gästen

Effects of side chains of oxatub[4]arene on its conformational interconversion, molecular recognition and macroscopic self-assembly.

A series of oxatub[4]arenes with different alkyl side chains have been synthesized. The conformational interconversion, molecular recognition and macroscopic self-assembly behaviour of oxatub[4]arene derivatives were investigated. The difference in side chains slightly changes the binding affinities, but results in different self-assembly morphologies at the solid state.

Direct High-Performance Liquid Chromatographic Separation of Peptide Enantiomers:  Study on Chiral Recognition by Systematic Evaluation of the Influence of Structural Features of the Chiral Selectors on Enantioselectivity

All-R/all-S enantiomers of oligoalanines (Ala(n), n = 1-10) with N-terminal protection group have been separated by HPLC on chiral stationary phases based on various cinchona alkaloid selectors. Structure-enantioselectivity relationships derived by extensive selector structure optimization provided insights into binding mechanisms and chiral recognition. Their interpretation was supported by X-ray crystal structures of amino acid and dipeptide, respectively, in complex with chiral selector. Optimized selectors have bulky elements representing steric barriers and deep binding pockets that afforded very high enantioselectivities; e.g., for the all-R and all-S enantiomers of N-(3,5-dinitrobenz…

Synthesis of Polycyclic Indolines by Utilizing a Reduction/Cyclization Cascade Reaction

European journal of organic chemistry 2021(45), 6097-6101 (2021). doi:10.1002/ejoc.202101191

Halogen bonds in 2,5-dihalopyridine-copper(II) chloride complexes

Ten coordination complexes obtained through a facile reaction between 2,5-dihalopyridines and copper(II) chloride (CuCl2) are characterized using single crystal X-ray diffraction. Two series of dihalopyridine complexes based on 2-chloro-5-X-pyridine and 2-bromo-5-X-pyridine (X = F, Cl, Br and I) were prepared to analyze the C–X2/X5⋯Cl–Cu halogen bonds (XB). The influence of X2- and X5-substituents on the respective interactions was examined by comparing them to the X2/X3⋯Cl–Cu XBs found in mono-substituted halopyridine complexes, (n-X-pyridine)2·CuCl2 (n = 2, 3 and X = Cl, Br and I). Varying the X5-halogens in (2,5-dihalopyridine)2·CuCl2, the C5–X5⋯Cl–Cu XBs follow the order F5 1 and they c…

Encapsulation of Et3N+–H···OH2 in a hydrogen-bonded resorcarene capsule

In the crystalline state a resorcarene dimer linked by ten hydrogen-bonding water molecules encapsulates the hydrogen-bonded complex Et3N+–H···OH2 while bromide anions are positioned outside the cavity.

1,2,6-Thiadiazine 1-Oxides: Unsaturated Three-Dimensional S,N-Heterocycles from Sulfonimidamides.

Unprecedented three-dimensional 1,2,6-thiadiazine 1-oxides have been prepared by an aza-Michael-addition/cyclization/condensation reaction sequence starting from sulfonimidamides and propargyl ketones. The products have been further functionalized by standard cross-coupling reactions, selective bromination of the heterocyclic ring, and conversion into a β-hydroxy substituted derivative. A representative product was characterized by single-crystal X-ray structure analysis. peerReviewed

Conformational changes in Cmethyl-resorcinarene pyridine N -oxide inclusion complexes in the solid state

Aromatic N-oxides interact with Cmethyl-resorcinarene resulting in marked changes in the conformation of the host resorcinarene. In the solid state, 2- and 3-methylpyridine N-oxides form pseudo-capsular 2 : 2 endo host-guest complexes with Cmethyl-resorcinarene stabilized by C-H⋯π interactions. The Cmethyl-resorcinarene·2-methylpyridine N-oxide complex has a C4v crown conformation, while the Cmethyl-resorcinarene·3-methylpyridine N-oxide complex has a slightly open C2v boat conformation. On the contrary, other para-substituted and benzo-fused pyridine N-oxides form only exo complexes with Cmethyl-resorcinarene. In the exo complexes, the asymmetry of the guest, conformational flexibility and…

From self-inclusion and host-guest complexes to channel structures

Various supramolecular interactions are applied as driving forces in self-assembly and molecular recognition processes. Single crystal X-ray diffraction method is especially important for solid-state studies of non-covalent interactions as it reveals their influence on the molecular and supramolecular structures. This paper discusses structures of two completely different types of compounds in which a variety of intermolecular interactions are involved. It will be shown that strong and weak intermolecular hydrogen bonds in N-alkylammonium resorcinarene salts, depending on the type of anion, inclusion of resorcinarene upper rim pendant group or solvent molecules into the cavity, strongly aff…

A synthetic molecular pentafoil knot

Knots are being discovered with increasing frequency in both biological and synthetic macromolecules and have been fundamental topological targets for chemical synthesis for the past two decades. Here, we report on the synthesis of the most complex non-DNA molecular knot prepared to date: the self-assembly of five bis-aldehyde and five bis-amine building blocks about five metal cations and one chloride anion to form a 160-atom-loop molecular pentafoil knot (five crossing points). The structure and topology of the knot is established by NMR spectroscopy, mass spectrometry and X-ray crystallography, revealing a symmetrical closed-loop double helicate with the chloride anion held at the centre…

Chiral Self‐Sorting of trans ‐Chelating Chiral Ligands upon Formation of Pd II Complexes (Eur. J. Inorg. Chem. 15/2014)

Adamantan als Baustein neuer Araliphane Synthese, Spektroskopie und Kristallstrukturen

Adamantane as a Building Block of New Araliphanes – Synthesis, Spectroscopy, and Crystal Structures Exchange of benzene units for aliphatic building blocks in cyclophanes leads to new molecules of the “araliphane” type. With adamantane the araliphanes 2 – 4 are synthesized. Their stereochemical behavior as shown by NMR studies and X-ray crystallographic analyses differs significantly from that of their aromatic counterparts. The signals of the intraannular adamantane hydrogens are strongly shifted upfield up to δ=– 2.18 (in 2). 4 is obtained as a racemic mixture of enantiomers (in the crystalline state) and shows a boat-like deformation of the benzene moiety.

Hydrogen bond-stabilised N-alkylammonium resorcinarene halide cavitands

A family of hydrogen bond-stabilised N-alkylammonium resorcinarene chloride and bromide cavitands were synthesised and characterised with 1H NMR and ESI mass spectrometry. The seven compounds exhibit interestingly either self-inclusion or guest complexation in the solid state evidenced by single crystal X-ray diffraction. The four dimers show self-inclusion of the upper rim propyl chains and consist of two hydrogen-bonded resorcinarene tetracations and six halide anions, while the remaining two halide anions are located in between the dimers linking them via hydrogen bonding. Small solvent molecules such as dichloromethane, methanol, n-butanol or chloroform are complexed into the resorcinar…

Self-assembly and anion encapsulation properties of cavitand-based coordination cages.

Two novel classes of cavitand-based coordination cages 7a--j and 8a--d have been synthesized via self-assembly procedures. The main factors controlling cage self-assembly (CSA) have been identified in (i) a P--M--P angle close to 90 degrees between the chelating ligand and the metal precursor, (ii) Pd and Pt as metal centers, (iii) a weakly coordinated counterion, and (iv) preorganization of the tetradentate cavitand ligand. Calorimetric measurements and dynamic (1)H and (19)F NMR experiments indicated that CSA is entropy driven. The temperature range of the equilibrium cage-oligomers is determined by the level of preorganization of the cavitand component. The crystal structure of cage 7d r…

Di-, Tri-, and Tetra(pentafluorophenyl) Derivatives for Oligotopic Anion−π Interactions

The present study describes a series of pentafluorobenzyl ammonium salts with two, three, or four C6F5 units in order to investigate simultaneous interactions of several perfluorinated arenes with anions in the crystalline state. Most of the structures show multiple anion-π contacts. However, only 6·2HI reveals an effective encapsulation of the iodide ion by the aromatic units. For comparison, the structure of 4b is investigated because it offers two π-systems with inverse charge distribution to a bromide anion. Only the electron-deficient π-system of the pentafluorophenyl group interacts with the anion.

Ion-Pair Complexation with Dibenzo[21]Crown-7 and Dibenzo[24]Crown-8 bis-Urea Receptors

Synthesis and ion-pair complexation properties of novel ditopic bis-urea receptors based on dibenzo[21]crown-7 (R(1) ) and dibenzo[24]crown-8 (R(2) ) scaffolds have been studied in the solid state, solution, and gas phase. In a 4:1 CDCl3 /[D6 ]DMSO solution, both receptors clearly show positive heterotropic cooperativity toward halide anions when complexed with Rb(+) or Cs(+) , with the halide affinity increasing in order I(-) <Br(-) <Cl(-) . In solution, the rubidium complexes of both receptors have higher halide affinities compared to the caesium complexes. However, Rb(+) and Cs(+) complexes of R(2) show stronger affinities toward all the studied anions compared to the corresponding catio…

Single and Multiple Additions of Dibenzoylmethane onto Buckminsterfullerene

A novel dibenzoylmethane-fullerene e,e,e-tris adduct was synthesized by the application of a variation of the Bingel–Hirsch conditions and characterized among others by X-ray crystallography. In addition, the corresponding hexakis adduct was detected by MALDI-TOF-MS analysis. Its existence was supported by density-functional-theory (DFT) computations. Furthermore a new synthesis of bis(benzoyl)methanofullerene was established, and its molecular structure was elucidated by X-ray crystallography. DFT computations reproduced the experimentally determined conformation and predict a low energy barrier for the rotation of the two benzoyl moieties.

Water-Soluble Cuprizone Derivative: Synthesis, Characterization, and in Vitro Studies

The cuprizone mouse model is one of the most accepted model systems for the investigation of oligodendrocyte degeneration, a process critically involved in the pathogenesis of diseases such as multiple sclerosis or schizophrenia. In order to substitute the in vivo experiments by in vitro approaches, the amine derivative BiMPi is introduced as a water-soluble alternative to cuprizone. Regarding superoxide dismutase activity, toxicity for oligodendrocytes, and disturbance of mitochondrial membrane potential, BiMPi shows similar in vitro effects as is observed in vivo for cuprizone. peerReviewed

Three-Component Entanglements Consisting of Three Crescent-Shaped Bidentate Ligands Coordinated to an Octahedral Metal Centre

3,3'-biisoquinoline ligands (biiq) L, bearing aromatic substituents on their 8 and 8' positions, have been used to generate interwoven systems consisting of three crescent-shaped ligands disposed around an octahedral metal centre. Mono-ligand complexes of the type [ReL(CO)3py]+ (py: pyridine) have also been prepared, leading to sterically non-hindering complexes in spite of the endotopic nature of the chelate used. The three-component entanglements have been prepared by using either FeII or RuII as gathering metal centre. The synthetic procedure is simple and efficient, affording fully characterised complexes as their PF6 or SbCl6 salts. X-ray crystallography clearly shows that the crescent…

Room-Temperature Phosphorescence and Efficient Singlet Oxygen Production by Cyclometalated Pt(II) Complexes with Aromatic Alkynyl Ligands

The synthesis of five novel cyclometalated platinum(II) compounds containing five different alkynyl-chromophores was achieved by the reaction of the previously synthesized Pt–Cl cyclometalated compound (1) with the corresponding RC≡CH by a Sonogashira reaction. It was observed that the spectral and photophysical characteristics of the cyclometalated platinum(II) complexes (Pt–Ar) are essentially associated with the platinum-cyclometalated unit. Room-temperature emission of the Pt–Ar complexes was attributed to phosphorescence in agreement with DFT calculations. Broad nanosecond (ns)-transient absorption spectra were observed with decays approximately identical to those obtained from the emi…

[3.3]Metacyclophane mit anti ‐Konformation

[3.3]Metacyclophanes with anti Conformation The [3.3]metacyclophanes 5 and 9 with prevailing anti conformation were prepared by using different cyclisation techniques. 1H-NMR studies and X-ray structure analyses of both phanes 5 and 9 prove their unprecedented conformations.

Self-Assembly of M24L48 Polyhedra Based on Empirical Prediction

Crystallography of encapsulated molecules.

The crystallography of supramolecular host–guest complexes is reviewed and discussed as a part of small molecule crystallography. In these complexes, the host binds the guests through weak supramolecular interactions, such as hydrogen and halogen bonding, cation–π, anion–π, C–H–π, π–π, C–H–anion interactions and the hydrophobic effect. As the guest often shows severe disorder, large thermal motion and low occupancies, the reliable crystallographic determination of the guest can be very demanding. The analysis of host–guest interactions using tools such as Hirshfeld and cavity volume surface analysis will help to look closely at the most important host–guest interactions. The jewel in the cr…

Halogen and Hydrogen Bonded Complexes of 5-Iodouracil

Three derivatives of 5-iodouracil were prepared, and their complexation properties, supplemented by 5-iodouracil under the same conditions, were studied with and without halogen bond acceptors in N,N-dimethylformamide, N,N-diethylformamide, N-methylformamide, formamide, dimethylsulfoxide, and water. The intermolecular halogen and hydrogen bonding interactions observed in the solid state were investigated using single crystal X-ray diffraction and quantum chemical calculations, and the acquired data were contrasted with bonding interactions previously reported for 5-iodouracil in the Cambridge Structural Database. It was found that the polarized iodine atom and the amidic NH functionality ac…

Equipping metallo-supramolecular macrocycles with functional groups: Assemblies of pyridine-substituted urea ligands

A series of di-(m-pyridyl)-urea ligands were prepared and characterized with respect to their conformations by NOESY experiments and crystallography. Methyl substitution in different positions of the pyridine rings provides control over the position of the pyridine N atoms relative to the urea carbonyl group. The ligands were used to self-assemble metallo-supramolecular M(2)L(2) and M(3)L(3) macrocycles which are generated in a finely balanced equilibrium in DMSO and DMF according to DOSY NMR experiments and ESI FTICR mass spectrometry. Again, crystallography was used to characterize the assemblies. Methyl substitution in positions next to the pyridine nitrogen prevents coordination, while …

The Preparation of Diaryl Sulfoxonium Triflates and Their Application in Palladium‐Catalyzed Cross‐Coupling Reactions

Chemistry 17(19), e202200828 (2022). doi:10.1002/asia.202200828

Recognition of Li+ by a Salophen−UO2 Homodimeric Complex

Self-assembly via mutual U-coordination of the salophen-UO(2) complex 1 creates a dimeric species which is shown to be useful for metal binding. Indeed, the 1 dimer has affinity for alkali metal cations and, interestingly, a marked selectivity for Li(+), determined by electrospray ionization mass spectrometry and (1)H NMR techniques. X-ray diffraction helped in the elucidation of the dimeric complex structure, which presents a crown-ether-type coordination site, in analogy to the more familiar 12-crown-4, responsible for the metal interaction. Comparison with isomer 2, and the salen derivative 3, increases the understanding of the behavior of such systems in solution and in the solid state.

Experimental investigation of anion-π interactions : Applications and biochemical relevance

Chemical communications 52(9), 1778 - 1795(2016). doi:10.1039/C5CC09072E

High-affinity and selective detection of pyrophosphate in water by a resorcinarene salt receptor

N-Alkyl ammonium resorcinarenes selectively bind pyrophosphate in pure water with an exceptionally high binding constant of up to 1.60 × 107 M–1, three orders of magnitude higher than ATP.

Ion Pair Binding in the Solid-State with Ditopic Crown Ether Uranyl Salophen Receptors

Two ditopic uranyl salophen receptors with benzo-15-crown-5 and benzo-18-crown-6 units (R(1) and R(2), respectively) have been synthesized from commercially available starting materials. Comprehensive studies on the solid-state ion pair complexation with various alkali and ammonium halides have been conducted. From the 19 obtained solid-state structures (6 structures with R(1), 13 structures with R(2)), three general interaction motifs I-III have been observed. Interaction motif I has a separated ion pair with the cation coordinated to the crown ether unit, and the anion or oxygen containing solvent molecule coordinated to the uranyl center. The interaction motif II manifests a polymeric st…

Selective recovery of gold from electronic waste using 3D-printed scavenger

Around 10% of the worldwide annual production of gold is used for manufacturing of electronic devices. According to the European Commission, waste electric and electronic equipment is the fastest growing waste stream in the European Union. This has generated the need for an effective method to recover gold from electronic waste. Here, we report a simple, effective, and highly selective nylon-12-based three-dimensional (3D)-printed scavenger objects for gold recovery directly from an aqua regia extract of a printed circuit board waste. Using the easy to handle and reusable 3D-printed meshes or columns, gold can be selectively captured both in a batch and continuous flow processes by dipping …

Thiourea Organocatalysts as Emerging Chiral Pollutants: En Route to Porphyrin-Based (Chir)Optical Sensing

Environmental pollution with chiral organic compounds is an emerging problem requiring innovative sensing methods. Amino-functionalized thioureas, such as 2-(dimethylamino)cyclohexyl-(3,5-bis(trifluoromethyl)phenyl)thiourea (Takemoto’s catalyst), are widely used organocatalysts with virtually unknown environmental safety data. Ecotoxicity studies based on the Vibrio fischeri luminescence inhibition test reveal significant toxicity of Takemoto’s catalyst (EC50 = 7.9 mg/L) and its NH2-substituted analog (EC50 = 7.2–7.4 mg/L). The observed toxic effect was pronounced by the influence of the trifluoromethyl moiety. En route to the porphyrin-based chemosensing of Takemoto-type thioureas, their s…

Substituent effects on axle binding in amide pseudorotaxanes: comparison of NMR titration and ITC data with DFT calculations

The binding behaviour of differently substituted diamide axle molecules to Hunter/Vögtle tetralactam macrocycles was studied with a combination of NMR titration, isothermal titration calorimetry (ITC) experiments and calculations employing density functional theory (DFT), along with dispersion-corrected exchange-correlation functionals. Guests with alkyl or alkenyl chains attached to the diamide carbonyl groups have a significantly higher binding affinity to the macrocycle than guests with benzoyl amides and their substituted analogues. While the binding of the benzoyl and alkenyl substituted axles is enthalpically driven, the alkyl-substituted guest binds mainly because of a positive bindi…

Mass spectrometric studies on small open-chain piperazine-containing ligands and their transition metal complexes

Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry was used to characterize the complexes formed between open-chain piperazine-containing ligands and transition metal salts (Cobalt, Copper, Zinc, and Cadmium as chlorides, nitrates, and acetates). Only single-charged complexes were observed, formed of one ligand (L) and mainly one metal ion (M). Since the net charge of the complexes was one, a counterion (X) was attached to some of the complexes, with formation of [L + M + X]+ complexes, and a proton was lost from others, as in [L − H + M]+ complexes. In most cases the composition of the complexes was more dependent on the ligand than the metal salt. Collisio…

Ethyl Pyrogallarene and Pyrogallarene: Synthesis, Structural Analysis and Derivatization

In the acid-catalyzed synthesis of ethyl pyrogall[4]arene, a novel hexamer, ethyl pyrogall[6] arene, is obtained as a readily isolable minor product. Pyrogall[6]arene can be isolated from the reaction mixture in three different ways yielding the hexamer in different forms and stabilities. Crystallization from DMSO and then recrystallization from acetone gives a stable crystalline solid, recrystallization directly from acetone yields an unstable white powder, while direct recrystallization from THF gives a stable white powder. Both pyrogall[4]arene and pyrogall[6]arene crystallize readily with DMSO filling the voids in the crystal lattice. Co-crystallization studies of the hexamer isolated b…

Induced-Fit Molecular Recognition with Water-Soluble Cavitands

Synthesis of novel water-soluble cavitands 1 and 2 and their complexes—the caviplexes—is described. The solubility in water derives from four primary ammonium groups on the lower rim and eight secondary amide groups on the upper rim. Cavitands 1 and 2 exist as D2d velcraplex dimers in aqueous solution but the addition of lipophilic guests 15–24 induces conformational changes to the vase-like structures. The internal cavity dimensions are 8×10 A, and the exchange rates of guests in the caviplexes are slow on the NMR timescale (room temperature and 600 MHz). The direct observation of bound species and the stoichiometry of the complexes is reported. The association constants (Ka) between 0.4×1…

Association of N-(Pyridin-2-yl),N′-substituted Ureas with 2-Amino-1,8-naphthyridines and Benzoates: NMR and Quantum Chemical Studies of the Substituent Effect on Complexation

Association of four N-(pyridin-2-yl),N'-R(1)-ureas (R(1) = ethyl, n-butyl, phenyl, and tert-butyl) with substituted 2-amino-1,8-naphthyridines and benzoates were studied by (1)H NMR spectroscopic titrations and quantum chemical calculations. The benzoates and 2-amino-1,8-naphthyridines were selected as representatives of double and triple hydrogen bonding counterparts, respectively. The classical substituent effect on the association was studied. A prerequisite and a crucial step for the complex formation was the breaking of the intramolecular hydrogen bond in urea derivatives. The QTAIM calculation method was employed to explain the hydrogen bonding within complexes. In the case of benzoat…

Selective Synthesis of Z -Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones

Journal of the American Chemical Society : JACS 143(22), 8375-8380 (2021). doi:10.1021/jacs.1c01797

CH-Directed Anion-π Interactions in the Crystals of Pentafluorobenzyl-Substituted Ammonium and Pyridinium Salts

Simple pentafluorobenzyl-substituted ammonium and pyridinium salts with different anions can be easily obtained by treatment of the parent amine or pyridine with the respective pentafluorobenzyl halide. Hexafluorophosphate is introduced as the anion by salt metathesis. In the case of the ammonium salt 4, water co-crystallisation seems to suppress effective anion-pi interactions of bromide with the electron-deficient aromatic system, whereas with salts 5 and 6 such interactions are observed despite the presence of water. However, due to asymmetric hydrogen-bonding interactions with ammonium side chains, the anion of 5 is located close to the rim of the pentafluorophenyl group (eta(1) interac…

Solid‐state NMR Spectroscopy of Iodine(I) Complexes

Solid-state NMR has been applied to a series of Barluenga-type iodine(I) [L-I-L]PF6 (L=pyridine, 4-ethylpyridine, 4-dimethylaminopyridine, isoquinoline) complexes as their hexafluorophosphate salts, as well as their respective non-liquid ligands (L), their precursor silver(I) complexes, and the respective N-methylated pyridinium and quinolinium hexafluorophoshate salts. These results are compared and contrasted to the corresponding solution studies and single-crystal X-ray structures. As the first study of its kind on the solid-state NMR behavior of halogen(I) complexes, practical considerations are also discussed to encourage wider utilization of this technique in the future. peerReviewed

Electrocrystallization of Monolayer-Protected Gold Clusters : Opening the Door to Quality, Quantity, and New Structures

Thiolate-protected metal clusters are materials of ever-growing importance in fundamental and applied research. Knowledge of their single-crystal X-ray structures has been instrumental to enable advanced molecular understanding of their intriguing properties. So far, however, a general, reliable, chemically clean approach to prepare single crystals suitable for accurate crystallographic analysis was missing. Here we show that single crystals of thiolate-protected clusters can be grown in large quantity and very high quality by electrocrystallization. This method relies on the fact that charged clusters display a higher solubility in polar solvents than their neutral counterparts. Nucleation…

Optimizing the SYBR green related cyanine dye structure to aim for brighter nucleic acid visualization

In recent years, the studies of RNA and its use for the development of RNA based vaccines have increased drastically. Although cyanine dyes are commonly used probes for studying nucleic acids, in a wide range of applications, there is still a growing need for better and brighter dyes. To meet this demand, we have systematically studied the structure of SYBR green-related cyanine dyes to gain a deeper understanding of their interactions with biomolecules especially how they interact with nucleic acids and the structural components which makes them strongly fluorescent. Herein, five new dyes were synthesized, and their photophysical properties were evaluated. Observations of photophysical cha…

Nonporous Organic Solids Capable of Dynamically Resolving Mixtures of Diiodoperfluoroalkanes

Halogen bonding has increasingly facilitated the assembly of diverse host-guest solids. Here, we show that a well-known class of organic salts, bis(trimethylammonium) alkane diiodides, can reversibly encapsulate α,ω-diiodoperfluoroalkanes (DIPFAs) through intermolecular interactions between the host's I – anions and the guest's terminal iodine substituents. The process is highly selective for the fluorocarbon that forms an I – ···I(CF 2 ) m I···I – superanion that is matched in length to the chosen dication. DIPFAs that are 2 to 12 carbons in length (common industrial intermediates) can thereby be isolated from mixtures by means of crystallization from solution upon addition of the dissolv…

CH-Anion versus anion-π interactions in the crystal and in solution of pentafluorobenzyl phosphonium salts

A series of phosphonium salts with pentafluorobenzyl substituents have been synthesized and were investigated in the crystal as well as in solution. The solid state structures of 1a, 1b and 2d reveal the presence of anion-π as well as CH-anion interactions. The two attractive, yet competitive forces seem to act in concert and a directing effect of the CH interaction on the relative position between anion and π-system is observed. The search for anion-π interactions in solution failed. Only CH-anion interactions proved to be important in solution.

Anion Receptors Based on a Quinoline Backbone

2-Amido-8-urea substituted quinoline derivatives are potent receptors for the binding of halide or benzoate anions in chloroform. The selectivity and affinity of the receptors for fluoride can be tuned by variation of the substituents at the receptor side chains. Computational considerations show that the cleft of the receptors provides space for effective binding of F–, but not bigger anions.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Strategies for Exploring Functions from Dynamic Combinatorial Libraries

Entrapment of a linear water pentamer into a uranyl-salophen dimer in the solid state

In the solid state, uranyl-salophen complex 1, decorated with bipyridyl sidearms, self-assembles from moist acetonitrile into dimeric species displaying a confined water pentamer, as observed by X-ray diffraction on single crystals. The linear water cluster is incarcerated within the dimeric cavity by coordination to the Lewis acidic uranyl centres and by a network of hydrogen bonds established with the pyridinic nitrogen atoms on the sidearms.

Ammonium ion mediated resorcarene capsules: ESI-FTICRMS study on gas-phase structure and ammonium ion affinity of tetraethyl resorcarene and its per-methylated derivative

AbstractThe ammonium ion binding affinities of tetraethyl resorcarene (1) and its per-methylated derivative (2) were studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Ten different ammonium ions were tested as guests for the resorcarenes. A strong tendency for complex formation was observed with all ammonium ions of size and charge distribution suitable for noncovalent interactions with the cavities of the resorcarene hosts 1 and 2. Although differences in ammonium ion affinities were observed between 1 and 2 due to the dissimilar conformations, the overall tendency was that increase in the degree of substitution and the length of ca…

Sterically and guest-controlled self-assembly of calix[4]arene derivatives.

In solvents such as chloroform or benzene, tetraurea calix[4]arenes 1 form dimeric capsules in which one solvent molecule is usually included as guest. To explore the structural requirements for the formation of such hydrogen-bonded dimers we replaced one p-tolylurea residue by a simple acetamide function. The resulting calix[4]arene 2 a, substituted at its wide rim with one acetamide and three p-tolylurea functions, assumes a C(1)-symmetrical conformation in apolar solvents as shown by (1)H NMR, which is not compatible with the usual capsule. In the crystalline state, four molecules of 2 a, adopting a pinched cone conformation, assemble into a quasi S(4)-symmetrical tetramer stabilized by …

Mass spectrometric studies of benzoxazine resorcarenes

Eleven differently substituted 3,4-dihydro-2H-1,3-benzoxazine resorcarenes were studied by electrospray ionisation (ESI) and matrix-assisted laser desorption/ionisation (MALDI) mass spectrometry, using Fourier transform ion cyclotron resonance (FT-ICR) and time-of-flight (TOF) mass spectrometers, respectively. Under ESI conditions it was possible to transfer the intact resorcarenes from solution to the gas phase, yielding [M + H]+ and [M + 2H]+ ions as the main ions observed. Energy increase of the ions induced ready decomposition through successive eliminations of four CH2NR groups. Ion-molecule reactions showed that the ionising proton was situated somewhere inside the molecule and could …

Synthesis and X-ray structure of amide-based macrocycles, catenanes and pretzelane

The syntheses and crystal structure studies of amide-based catenanes derived from m-phenylene diacrylic acid and 5-acetoxy isophthalic acid (17% and 3% yield of 4a and 4b resp.) and octalactam macrocycles (21% yield of 3) are described. Hydrogen bonding patterns play a key role in the formation of the different conformations of octalactam 3. The crystal structures of 3 reveal a number of hydrogen-bonding interactions between the macrocycle and two different solvent molecules, which are presumably responsible for the different conformations. Furthermore, we report the X-ray structure of a catenane, which was converted into a “pretzelane” by bridging two phenolic hydroxy groups with a p-xylyl…

Hierarchical halogen bonding induces polymorphism

Co-crystals of 1-iodo-3,5-dinitrobenzene and 1,4-diazabicyclo[2.2.2]octane manifest either two strong or one strong and one weak intermolecular 2 : 1 halogen bond (XB) motifs in polymorphic structures I and II, respectively, whereas weaker XB-donor 4,4-bipyridine just forms 1 : 1 structure III with one strong halogen bond.

A copper-catalyzed interrupted domino reaction for the synthesis of fused triazolyl benzothiadiazine-1-oxides

Chemistry - a European journal 29(13), e202203729 (2023). doi:10.1002/chem.202203729

Evaluation of multivalency as an organization principle for the efficient synthesis of doubly and triply threaded amide rotaxanes

Mono-, di- and trivalent pseudorotaxanes with tetralactam macrocycle hosts and axles containing diamide binding stations as the guests have been synthesised. Their threading behaviour was analyzed in detail by NMR experiments and isothermal titration calorimetry. An X-ray crystal structure of the monovalent pseudorotaxane confirms the binding motif. Double mutant cycle analysis provides the effective molarities and insight into the chelate cooperativity of multivalent binding. While the second binding event in a trivalent pseudorotaxane exhibits a slightly positive cooperativity, the third binding is nearly non-cooperative. Nevertheless, the enhanced binding affinities resulting from the mu…

Enantiomerically pure trinuclear helicates via diastereoselective self-assembly and characterization of their redox chemistry.

A tris(bipyridine) ligand 1 with two BINOL (BINOL = 2, 2′-dihydroxy-1, 1′-binaphthyl) groups has been prepared in two enantiomerically pure forms. This ligand undergoes completely diastereoselective self-assembly into D2-symmeteric double-stranded trinuclear helicates upon coordination to copper(I) and silver(I) ions and to D3-symmetric triple-stranded trinuclear helicates upon coordination to copper(II), zinc(II), and iron(II) ions as demonstrated by mass spectrometry, NMR and CD spectroscopy in combination with quantum chemical calculations and X-ray diffraction analysis. According to the calculations, the single diastereomers that are formed during the self-assembly process are strongly …

Synthesis, characterization and thermal behavior of nine new -type quaternary ammonium tetrafluoroborate or hexafluorophosphate salts prepared by metathesis from analogous halide salts

Abstract Nine new quaternary ammonium tetrafluoroborate or hexafluoroborate salts were prepared from analogous bromide or chloride salts using anion exchange reaction in which the corresponding bromide or chloride salt was treated with HBF4 or HPF6 acid in aqueous solutions. The characterizations were performed by 1H NMR and 13C NMR spectroscopy as well as by elemental analysis. The single crystals of three tetrafluoroborate and two hexafluorophosphate salts were obtained by slow evaporation from a methanol/ethyl acetate solution and the crystal structures were determined by X-ray single crystal diffraction. Four of the compounds crystallized in the orthorhombic and one in the monoclinic cr…

Binding Profiles of Self-Assembled Supramolecular Cages from ESI-MS Based Methodology

Confined molecular environments have peculiar characteristics that make their properties unique in the field of biological and chemical sciences. In recent years, advances in supramolecular capsule and cage synthesis have presented the possibility to interpret the principles behind their self‐assembly and functions, which has led to new molecular systems that display outstanding properties in molecular recognition and catalysis. Herein, we report a rapid method based on ESI‐MS to determine the binding profiles for linear saturated dicarboxylic acids in a series of different cages. The cages were obtained by self‐assembly of modified tris(pyridylmethyl)amine (TPMA) complexes and diamines cho…

A novel MALDI-MS approach for the analysis of neutral metallosupramolecular architectures

Matrix assisted laser desorption/ionisation mass spectrometry (MALDI-MS) methods have been developed for the characterisation of neutral [2×2] metallogrids derived fromdiimine, dihydrazone and diacylhydrazone ligands. Such grids may be protonated in solution to give cationic species but in most cases these are labile, so that rather delicate conditions are required for observation of the intact metallogrids as monoprotonated derivatives in the gas phase. As a MALDI matrix, 2,4,6-trihydroxyacetophenone (THAP) is sufficiently acidic to enable monoprotonation of the grids unaccompanied by dissociation, and if the grid sample is initially deposited by a layering technique to avoid any prelimina…

Durch Temperatur, Druck oder Licht induzierter Spinübergang in einer supramolekularen Fe‐[2×2]‐Gitterverbindung

Covalently linked multi-calixarenes

Abstract ipso-Nitration of t-butyl calix[4]arene tetraethers and subsequent hydrogenation provides an easy access to monoamino calix[4]arenes. Reaction with di- and triacid chlorides leads to various double- and triple-calix[4]arenes. With tetraacid chlorides derived from calix[4]arenes in the cone- or 1,3-alternate-conformations penta-calix[4]arenes are available as molecularly uniform species, which may be regarded as the first generation of calix[4]arene based dendrimers. The structure of the mononitro tetraester derivative, which may serve as a general building block has been confirmed by single crystal X-ray analysis.

Chemistry and Photochemistry of 2,6-Bis(2-hydroxybenzilidene)cyclohexanone. An Example of a Compound Following the Anthocyanins Network of Chemical Reactions

The kinetics and thermodynamics of the 2,6-bis(2-hydroxybenzilidene)cyclohexanone chemical reactions network was studied at different pH values using NMR, UV-vis, continuous irradiation, and flash photolysis. The chemical behavior of the system partially resembles anthocyanins and their analogue compounds. 2,6-Bis(2-hydroxybenzilidene)cyclohexanone exhibits a slow color change from yellow to red styrylflavylium under extreme acidic conditions. The rate constant for this process (5 × 10(-5) s(-1)) is pH independent and controlled by the cis-trans isomerization barrier. However, the interesting feature is the appearance of the colorless compound, 7,8-dihydro-6H-chromeno[3,2-d]xanthene, isolat…

CF3: An Electron-Withdrawing Substituent for Aromatic Anion Acceptors? “Side-On” versus “On-Top” Binding of Halides

The ability of multiple CF3 -substituted arenes to act as acceptors for anions is investigated. The results of quantum-chemical calculations show that a high degree of trifluoromethyl substitution at the aromatic ring results in a positive quadrupole moment. However, depending on the polarizability of the anion and on the substitution at the arene, three different modes of interaction, namely Meisenheimer complex, side-on hydrogen bonding, or anion-π interaction, can occur. Experimentally, the side-on as well as a η(2) -type π-complex are observed in the crystal, whereas in solution only side-on binding is found.

Encapsulation of diquats by resorcinarenes: a novel staggered anion–solvent mediated hydrogen bonded capsule

Crystallisation studies of ethyl resorcinarene with diquats 2b and 3a (1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane dibromide and 1,4-diazoniabicyclo[2.2.2]octane dichloride, respectively) resulted in hydrogen bonded molecular capsules in which the cations are encapsulated in between the cavities of two resorcinarene molecules and anions are located in the middle of the lower rim ethyl chains.

Ein makrobicyclischer Tris-bipyridin-Ligand sowie ein Cu2I- und ein Ag3I-Komplex

A supramolecular system that strictly follows the binding mechanism of conformational selection

Induced fit and conformational selection are two dominant binding mechanisms in biology. Although induced fit has been widely accepted by supramolecular chemists, conformational selection is rarely studied with synthetic systems. In the present research, we report a macrocyclic host whose binding mechanism is unambiguously assigned to conformational selection. The kinetic and thermodynamic aspects of this system are studied in great detail. It reveals that the kinetic equation commonly used for conformational selection is strictly followed here. In addition, two mathematical models are developed to determine the association constants of the same guest to the two host conformations. A “confo…

Host-guest complexes of C-propyl-2-bromoresorcinarene with aromatic N-oxides*

The host-guest complexes of C-propyl-2-bromoresorcinarene with pyridine N-oxide, 3-methylpyridine N-oxide, quinoline N-oxide and isoquinoline N-oxide are studied using single crystal X-ray crystallography and 1H NMR spectroscopy. The C-propyl-2-bromoresorcinarene forms endo-complexes with the aromatic N-oxides in the solid-state when crystallised from either methanol or acetone. In solution, the endo-complexes were observed only in methanol-d4. In DMSO the solvent itself is a good guest, and crystallisation provides only solvate endo-complexes. The C-propyl-2-bromoresorcinarene shows remarkable flexibility when crystallised from either methanol or acetone, and packs into one-dimensional sel…

X-ray snapshot observation of palladium-mediated aromatic bromination in a porous complex

Pd-mediated aromatic bromination is intriguing to synthetic and organometallic chemists due to both its synthetic utility and, more importantly, a proposed mechanism involving an uncommon Pd(IV)/Pd(II) catalytic cycle. Here, we report an X-ray snapshot observation of a Pd reaction center during a Pd-mediated aromatic bromination in a single crystal of a porous coordination network crystalline scaffold. Upon treatment of a single crystal with N-bromosuccinimide, sequential X-ray snapshots revealed that the aryl-Pd(II)-L species embedded in the network pores was converted to the brominated aryl product through a transient aryl-Pd(II)-Br species, which is normally unobservable because of its r…

Macrocyclic complexes based on [N⋯I⋯N]+ halogen bonds

New 1–2 nm macrocyclic iodine(I) complexes prepared VIA a simple ligand exchange reaction manifest rigid 0.5–1 nm cavities that bind the hexafluorophosphate anion in the gas phase. The size of the cavities and the electrostatic interactions with the iodine(I) cations influence the anion binding properties of these macrocyclic complexes.

Derivatisation of Pyrogallarenes

Derivatisation of upper-rim hydroxy groups of pyrogallarenes produced completely acylated and tosylated pyrogallarene derivatives. Mesitylation of pyrogallarene, however, resulted in a regioselective derivatisation of hydroxy groups, i.e. eight OH groups out of 12 were mesitylated. Crystal structures of the synthesised pyrogallarene derivatives indicate that completely substituted pyrogallarenes exist in a distorted crown conformation despite of the lack of stabilising intramolecular hydrogen bonds. In contrast, the partially substituted pyrogallarene adopts a boat conformation and has an open cavity for the inclusion of small guest molecules. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinh…

Systematic Modulation of the Supramolecular Gelation Properties of Bile Acid Alkyl Amides

The self-assembly properties of nine low-molecular-weight gelators (LMWGs) based on bile acid alkyl amides were studied in detail. Based on the results, the number of hydroxyl groups attached to the steroidal backbone plays a major role in the gelation, although the nature of the aliphatic side chain also modulates the gelation abilities. Of the 50 gel systems studied, 35 are based on lithocholic acid and 15 on cholic acid derivatives. The deoxycholic acid derivatives did not form any gels. The gelation occurred primarily in aromatic solvents and the gels manifested typical fibrous or spherical morphologies. The 13C cross-polarized magic angle spinning (CPMAS) NMR spectra measured on the cr…

Asymmetric Synthesis of Spiro Tetrahydrothiophene-indan-1,3-diones via a Squaramide-Catalyzed Sulfa-Michael/Aldol Domino Reaction

Synthesis 48(08), 1131-1138(2016). doi:10.1055/s-0035-1560412

Synthesis and characterization of polyene chromophores with hydroxyl functionalization

Abstract Eight hydroxyl functionalized donor–acceptor polyene chromophores 3–10 were synthesized and characterized. Knoevenagel condensation reaction of aromatic polyenals with 2-cyanoacetamide derivatives was utilized to synthesize chromophores with all-E configuration. Chromophores of this kind can be attached covalently to polymers or functionalized with dendrons in order to tune the properties. The structures of the molecules were verified by 1H NMR, 13C NMR, ESI-TOF mass spectrometry and UV–vis measurements. Reduced bond-length alternation of the molecules in DMSO-d6 solution were observed by calculating the average difference of the vicinal coupling constants between adjacent CH CH an…

X-Ray crystallographic and computational study on uranyl-salophen complexes bearing nitro groups.

In the solid state, salophen–UO2 complexes bearing one, two, or three NO2 groups lack the pronounced ligand curvature that represents a structural hallmark for this class of compounds. A detailed structural study based on single-crystal X-ray crystallography and computational methods, comprising molecular dynamics, gas-phase Hartree Fock, and DFT calculations, was carried out to investigate the coordination properties of the uranyl cation.

Synthesis, characterization and antimicrobial activity of palladium(II) complexes with some alkyl derivates of thiosalicylic acids: Crystal structure of the bis(S-benzyl-thiosalicylate)–palladium(II) complex, [Pd(S-bz-thiosal)2]

Abstract S-Alkyl (R = benzyl, methyl, ethyl, propyl and butyl) derivatives of thiosalicylic acid and the corresponding palladium(II) complexes were prepared and their structures were proposed on the basis of infrared, 1H and 13C NMR spectroscopy. The cis geometrical configurations of the isolated complexes were proposed on the basis of an X-ray structural study of the bis(S-benzyl-thiosalicylate)–palladium(II), [Pd(S-bz-thiosal)2] complex. Antimicrobial activity of the tested compounds was evaluated by determining the minimum inhibitory concentration (MIC) and minimum microbicidal concentration (MMC) in relation to 26 species of microorganisms. The tested ligands, with a few exceptions, sho…

Structural macrocyclic supramolecular chemistry

Anionen bindende Resorcinaren-Cavitanden: die Bedeutung von CH⋅⋅⋅Anion-Wechselwirkungen

Pyrene-Derived Novel One- and Two-Component Organogelators

A new class of alkyl-chain-appended pyrene derivatives 4-14 were synthesized and evaluated for their gelation abilities. Depending on the nature of the linking group, these compounds gelated a number of organic solvents, either in the presence or in the absence of the acceptor molecule 2,4,7-trinitrofluorenone (TNF). Compounds with ester, ether, or alkyl linkages gelated a number of hydroxylic and hydrocarbon solvents by means of a charge-transfer interaction with TNF, while compounds with amide, urethane and urea linkers formed gels on their own in a variety of solvents by means of pi-pi stacking and hydrogen-bonding interactions. The Xray crystal structure of urethane (S)-12 showed hydrog…

Bisfunctionalized Janus Molecules

[reaction: see text] Bisfunctionalized dendritic multiester molecules were synthesized by combined protection-deprotection and divergent-convergent-divergent sequences in high yields leading to dendritic molecules that combine two functionally different surfaces, polar aliphatic arborol and nonpolar gallate ether moieties, resulting in a two-faced Janus molecule.

Highly Enantioselective Kinetic Resolution of Michael Adducts through N-Heterocyclic Carbene Catalysis: An Efficient Asymmetric Route to Cyclohexenes

Ahighly efficient strategy for the kinetic resolu-tion of Michael adductswas realized using achiral N-het-erocyclic carbene catalyst.The kinetic resolution providesanew convenientroute to single diastereomers of cyclo-hexenes and Michael adducts in good yields with highenantiomeric excesses (up to 99 % ee with aselectivityfactor of up to 458). This “two flies with one swat” con-cept allows the synthesis of these two synthetically valua-ble compound classes at the same time by asingle trans-formation. peerReviewed

Sterically geared tris-thioureas; transmembrane chloride transporters with unusual activity and accessibility

Tris-N-arylthioureas derived in one step from 1,3,5-tris(aminomethyl)-2,4,6-triethylbenzene are remarkably effective anion carriers. With optimised aryl substituents their activities come close to the best currently known, suggesting that they might find use as readily available standards in anion transport research.

Secoiridoids and Iridoids from Morinda asteroscepa

The new 2,3-secoiridoids morisecoiridoic acids A (1) and B (2), the new iridoid 8-acetoxyepishanzilactone (3), and four additional known iridoids (4–7) were isolated from the leaf and stem bark methanol extracts of Morinda asteroscepa using chromatographic methods. The structure of shanzilactone (4) was revised. The purified metabolites were identified using NMR spectroscopic and mass spectrometric techniques, with the absolute configuration of 1 having been established by single-crystal X-ray diffraction analysis. The crude leaf extract (10 μg/mL) and compounds 1–3 and 5 (10 μM) showed mild antiplasmodial activities against the chloroquine-sensitive malaria parasite Plasmodium falciparum (…

Inside Cover: Efficient Self-Assembly of Di-, Tri-, Tetra-, and Hexavalent Hosts with Predefined Geometries for the Investigation of Multivalency (Chem. Eur. J. 37/2015)

A new isomer of [{Zn(IX)2(NO3)2}·2.5H2O]n [IX = 1,4-bis(imidazole-1-methylene)-benzene] as a rare example of topological isomerism in coordination polymers

Shedding Light on the Interactions of Hydrocarbon Ester Substituents upon Formation of Dimeric Titanium(IV) Triscatecholates in DMSO Solution

Abstract The dissociation of hierarchically formed dimeric triple lithium bridged triscatecholate titanium(IV) helicates with hydrocarbyl esters as side groups is systematically investigated in DMSO. Primary alkyl, alkenyl, alkynyl as well as benzyl esters are studied in order to minimize steric effects close to the helicate core. The 1H NMR dimerization constants for the monomer–dimer equilibrium show some solvent dependent influence of the side chains on the dimer stability. In the dimer, the ability of the hydrocarbyl ester groups to aggregate minimizes their contacts with the solvent molecules. Due to this, most solvophobic alkyl groups show the highest dimerization tendency followed by…

Synthesis, characterization and the first crystal structure of the Zn(II) complex of 4,6-O-ethylidine-N-(2-hydroxybenzylidene)-β-D-glucopyranosylamine

4,6-O-Ethylidine-N-(2-hydroxybenzylidene)-β-D-glucopyranosylamine (H3L1) and N-(5-bromo-2-hydroxybenzylidene-4,6-O-ethylidine-β-D-glucopyranosylamine (H3L2) molecules possessing a–C-1–N=C(H)–moiety for metal-ion binding were synthesized by condensing the 4,6–O–ethylidene–β–D–glucopyranosylamine with salicylaldehyde or 5–bromosalicylaldehyde. Complexes of these ligands with Zn(II) were isolated and characterized using elemental analysis, FTIR, UV–Vis absorption, NMR spectroscopic and FAB mass spectrometric techniques. The structure of the Zn(II) complex derived from H3L1 was established for the first time by a single-crystal X-ray diffraction study. The anomeric nature of the saccharide moie…

Synthesis of novel reactive coalescing agents and their application in a latex coating

The syntheses and the performance of five glycidyl compounds as novel reactive coalescing agents are presented. The reactive coalescing agents were synthesized with moderate yields, structures were verified using spectroscopic methods, and the properties of glycidyl compounds such as boiling points and evaporation rates were measured. The applicability of five glycidyl compounds as reactive coalescing agents was tested in characterized carboxyl functional latex. Properties like pendulum hardness, gloss, and efficiency of the glycidyl compound to reduce the minimum film-formation temperature (MFFT) of the latex were measured from the cured latex films. The application test results were compa…

Acetonitrile inclusion complexes of piperazine-based macrocycles

New piperazine-based macrocycles with single small cavities were prepared by using high dilution technique. The inclusion of acetonitrile into the cavity (7, 8) or clathrate formation (3) was studied by 1H-NMR spectroscopy in solution and by X-ray diffraction in the crystalline state. The cycle 3 forms a molecular cleft, a molecular pocket, where the acetonitrile molecule is held by four weak N…H interactions reinforcing the clathrate formation. The cycles 7 and 8 contain a rigid cavity for an exact sterical fit with the methyl group of a linear compound like acetonitrile. The acetonitrile inclusion complex with 7 proved to be stable under normal conditions and was studied by means of therm…

Solvent Exchange in Thermally Stable Resorcinarene Nanotubes

The assembly of C-methyl resorcinarene into a tubular supramolecular solid-state structure, its thermal stability, and its hosting properties are reported. Careful control of the crystallisation conditions of C-methyl resorcinarene and 1,4-dimethyl-1,4-diazoniabicyclo[2.2.2]octane (1,4-dimethyl DABCO) dibromide leads to a formation of two crystallographically different, but structurally very similar, solid-state nanotube structures. These structures undergo a remarkable variety of supramolecular interactions, which lead to the formation of 0.5 nm diameter nonpolar tubes through the crystal lattice. The formation of these tubes is templated by suitably sized small alcohols, namely, n-propano…

Carbonyl hypoiodites from pivalic and trimesic acid and their silver(I) intermediates

The first tris(O–I–N) carbonyl hypoiodites have been synthesised based on trimesic acid and pyridine or 4-methylpyridine, with their structures definitively confirmed by single crystal X-ray diffraction (SCXRD). The more soluble carbonyl hypoiodites based on pivalic acid have also been studied via NMR, SCXRD, and computational analyses, enabling the study of the direct silver(I) precursor and intermediates of the resulting carbonyl hypoiodites generated using a range of substituted pyridines. peerReviewed

Encapsulation and solid state sequestration of gases by calix[6]arene-based molecular containers

Two calix[6]arene-based molecular containers were synthesized in high yields. These containers can encapsulate small guests through a unique "rotating door" complexation process. The sequestration of greenhouse gases is clearly demonstrated. They can be stored in the solid state for long periods and released via dissolution of the inclusion complex.

A handy and accessible tool for identification of Sn(II) in toothpaste.

AbstractAn easily accessible colorimetric probe, a carbazole–naphthaldehyde conjugate (CNP), was successfully prepared for the selective and sensitive recognition of Sn(II) in different commercially-available toothpaste and mouth wash samples. The binding mechanism of CNP for Sn2+ was confirmed by UV–Vis, 1H, and 13C NMR titrations. The proposed sensing mechanism was supported by quantum chemical calculations. Selective detection of Sn(II) in the nanomolar range (85 nM), among other interfering metal ions, makes it exclusive. Moreover, Sn2+ can be detected with a simple paper strip from toothpaste, which makes this method handy and easily accessible. The potential application of this system…

Assembly and dichroism of a four-component halogen-bonded metal-organic cocrystal salt solvate involving dicyanoaurate(I) acceptors

We describe the use of dicyanoaurate ions as linear ditopic metal–organic acceptors for the halogen bond-driven assembly of a dichroic metal–organic cocrystal based on azobenzene chromophores. Structural analysis by single crystal X-ray diffraction revealed that the material is a four-component solid, consisting of anticipated anionic metal–organic halogen-bonded chains based on dicyanoaurate ions, as well as complex potassium-based cations and discrete molecules of the crown ether 15-crown-5. Importantly, the structural analysis revealed the parallel alignment of the halogen-bonded chains required for dichroic behaviour, confirming that crystal engineering principles developed for the desi…

Field-induced ferromagnetism due to magneto-striction in 1-D helical chains

Two homochiral copper(II) helices, [Cu(μ1,3-N3)(L1)]n (1) and [Cu(μ1,3-NCO)(L2)]n (2), with end-to-end pseudohalide bridges, were synthesized using two N2O donor achiral Schiff bases via spontaneous chiral resolution. Field-induced ferromagnetic ordering due to magneto-striction in homochiral 1-D helix [Cu(μ1,3-N3)(L1)]n (1) is reported for the first time. At temperatures below 5.5 K, under a magnetic field of 1 T, orthogonality between the magnetic orbitals of copper centres increases significantly due to the contraction of lattice parameters, giving rise to long-range ferromagnetic ordering in the helical chain. The magneto-dielectric results are also indicative of the observed magneto-st…

Formation of a novel ferromagnetic end-to-end cyanate bridged homochiral helical copper(ii) Schiff base complex via spontaneous symmetry breaking

A homochiral helical coordination polymer of copper(II) has been synthesized using achiral precursors via spontaneous symmetry breaking and has been confirmed by single crystal X-ray diffraction and solid-state CD spectroscopy. The variable temperature magnetic measurements indicate the presence of weak ferromagnetic exchange interactions mediated by end-to-end cyanate bridges (J = +0.12 cm(-1)).

Transition metal ion induced hydrogelation by amino-terpyridine ligands

Hydrogelation behavior of two amino-terpyridine ligands in the presence of divalent metal ions in water was studied in detail. The effect of ligand structure and different counter anions on the gel morphologies was also explored. peerReviewed

Efficient stabilisation of a dihydrogenphosphate tetramer and a dihydrogenpyrophosphate dimer by a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties† †In memoriam Fritz Vögtle (1939–2017). ‡ ‡Electronic supplementary information (ESI) available: Synthetic details, NMR spectroscopic and MS spectrometric characterisation of 2, NMR spectroscopic and mass spectrometric binding studies, ITC titrations, and crystal structures. CCDC 1555955–1555958. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc02700a Click here for additional data file. Click here for additional data file.

A cyclic pseudooctapeptide binds a dihydrogenpyrophosphate dimer or a cyclic dihydrogenphosphate tetramer by sandwiching these anionic aggregates between two pseudopeptide rings.

Substituent Effects on the [N−I−N]+ Halogen Bond

We have investigated the influence of electron density on the three-center [N–I–N]+ halogen bond. A series of [bis(pyridine)iodine]+ and [1,2-bis((pyridine-2-ylethynyl)benzene)iodine]+ BF4– complexes substituted with electron withdrawing and donating functionalities in the para-position of their pyridine nitrogen were synthesized and studied by spectroscopic and computational methods. The systematic change of electron density of the pyridine nitrogens upon alteration of the para-substituent (NO2, CF3, H, F, Me, OMe, NMe2) was confirmed by 15N NMR and by computation of the natural atomic population and the π electron population of the nitrogen atoms. Formation of the [N–I–N]+ halogen bond re…

N-Heterocyclic Carbene-Catalyzed Activation of α-Chloroaldehydes: Asymmetric Synthesis of 5-Cyano-Substituted Dihydropyranones

An N-heterocyclic carbene (NHC)-catalyzed asymmetric [4+2] annulation of (E)-2-benzoyl-3-phenylacrylonitriles with α-chloroaldehydes has been developed. The protocol leads to 5-cyano-substituted dihydropyranones in good to excellent yields with excellent diastereo- and enantioselectivities (up to 93% yield, &gt;20:1 d.r. and 99% ee).

Synthesis, characterization and solid-state photoluminescence studies of six alkoxy phenylene ethynylene dinuclear palladium(II) rods

A rare family of six discrete binuclear [PdCl(PEt3)2] phenylene ethynylene rods with alkoxy side chains (methoxy, ethoxy and heptoxy) have been developed, and their solid-state photoluminescence results have been presented and discussed. The shorter bridging ligands are of the general formula H–CuC– C6H2(R)2–CuC–H, where R = H, OCH3, OC 2H5, and OC7H15, whereas the longer ones are based on H– CuC–C6H4–CuC–C6H2(R)2–CuC–C6H4–CuC–H, where R = OCH3, OC 2H5. These ligands display increasing length in both the main dimension (backbone length) as well as the number of carbons in the side chains (R, alkoxide side chain) that stem from the central phenylene moiety. The X-ray crystal structures of tw…

Preparation and Characterization of Novel Poly(alkylidenamine) Nitrile Ruthenium Metallodendrimers

Complete functionalization of N,N,N',N'-[tetrakis(cyanoethyl)-hexamethylenediamine] [N≡C(CH 2 ) 2 ] 2 N(CH 2 ) 6 N[(CH 2 ) 2 -C≡N] 2 (4) and N,N,N',N'-(tetrakis(cyanoethoxypropyl)hexamethylenediamine] [N≡C(CH 2 ) 2 O(CH 2 ) 3 ] 2 N(CH 2 ) 6 N[(CH 2 ) 3 -O(CH 2 ) 2 C≡N] 2 (7) with the organometallic moiety [Ru(η 5 -C 5 H 5 )(PPh 3 ) 2 Cl] and the five-coordinate cis-[RuCl(dppe) 2 ]-[PF 6 ] [dppe = 1,2-bis(diphenylphosphanyl)ethane] was attained with good yield, respectively, by treating the metallo-fragment with the core in methanol (at room temperature and in presence of TIPF 6 as a chloride abstractor) and in 1,2-dichloroethane (under reflux). These novel nitrile-functionalized poly(alkyli…

Cooperative Binding of Divalent Diamides by N-Alkyl Ammonium Resorcinarene Chlorides

N-Alkyl ammonium resorcinarene chlorides, stabilized by an intricate array of hydrogen bonds leading to a cavitand-like structure, bind amides. The molecular recognition occurs through intermolecular hydrogen bonds between the carbonyl oxygen and the amide hydrogen of the guests and the cation-anion circular hydrogen-bonded seam of the hosts, as well as through CH⋅⋅⋅π interactions. The N-alkyl ammonium resorcinarene chlorides cooperatively bind a series of di-acetamides of varying spacer lengths ranging from three to seven carbons. Titration data fit either a 1:1 or 2:1 binding isotherm depending on the spacer lengths. Considering all the guests possess similar binding motifs, the first bin…

White Phosphorus Is Air-Stable Within a Self-Assembled Tetrahedral Capsule

Molecular Fire Quencher Cage-shaped molecular assemblies can regulate the reactivity of smaller molecules trapped within them. Mal et al. (p. 1697 ) extend this approach to enable the protection of elemental white phosphorus (P 4 ), a substance that rapidly ignites on contact with oxygen. The tetrahedral cages self-assemble in aqueous solution through coordination of six ligands to four iron ions, and efficiently capture phosphorus from a suspension. The water-soluble host-guest constructs were stable in air for at least 4 months, but released intact P 4 rapidly on displacement by added benzene.

One‐pot synthesis of [2+2]‐helicate‐like macrocycle and 2+4‐μ 4 ‐oxo tetranuclear open frame complexes: Chiroptical properties and asymmetric oxidative coupling of 2‐naphthols

Halogen bonds with coordinative nature: halogen bonding in a S–I+–S iodonium complex†

A detailed study of unexpectedly strong iodonium–sulfur halogen bonds in [I(2-imidazolidinethione)2]+ is presented. The interactions are characterized by single-crystal X-ray diffraction, charge density analysis based on QTAIM calculations, mass spectrometry, and NMR spectroscopy. The results, small RIS = 0.7 and high interaction energy of −60 kJ mol−1, support a coordinative nature of the halogen bond between the iodonium ion and the sp2 hybridized sulfur atoms.

An aryl-fused redox-active tetrathiafulvalene with enhanced mixed-valence and radical-cation dimer stabilities.

Molecular recognition of stable organic radicals is a relatively novel, but important structural binding motif in supramolecular chemistry. Here, we report on a redox-switchable veratrole-fused tetrathiafulvalene derivative VTTF which is ideally suited for this purpose and for the incorporation into stimuli-responsive systems. As revealed by electrochemistry, UV/Vis measurements, X-ray analysis, and electrocrystallisation, VTTF can be reversibly oxidised to the corresponding radical-cation or dication which shows optoelectronic and structural propterties similar to tetrathiafulvalene and tetrakis(methylthio)tetrathiafulvalene. However, theoretical calculations, variable temperature EPR, and…

Hydrogen-Bonded Analogues of Cavitands

Achieving Strong Positive Cooperativity through Activating Weak Non-Covalent Interactions

Positive cooperativity achieved through activating weak non-covalent interactions is common in biological assemblies but is rarely observed in synthetic complexes. Two new molecular tubes have been synthesized and the syn isomer binds DABCO-based organic cations with high orientational selectivity. Surprisingly, the ternary complex with two hosts and one guest shows a high cooperativity factor (α=580), which is the highest reported for synthetic systems without involving ion-pairing interactions. The X-ray single-crystal structure revealed that the strong positive cooperativity likely originates from eight C-H⋅⋅⋅O hydrogen bonds between the two head-to-head-arranged syn tube molecules. Thes…

Highlights on contemporary recognition and sensing of fluoride anion in solution and in the solid state

The fluoride anion has recently gained well deserved attention among the scientific community for its importance in many fields of human activities, but also for concerns on its effect on health and the environment. Although surprisingly overlooked in systematic studies in the past, fluoride has nowadays become a topical target in the field of anion recognition. A multitude of scientific reports are published every year where the establishment of efficient and specific interaction with fluoride is sought in polar and aqueous media. Here, the emphasis is directed to a detailed description of the most interesting contemporary studies in the field, with a particular focus given to those publis…

[2,6-Bis(di-tert-butylphosphinomethyl)phenyl-κ3P,C1,P′](trifluoroacetato)palladium(II)

The Pd(II) atom in the title compound, [Pd(C(2)F(3)O(2))(C(24)H(43)P(2))], adopts a distorted square-planar geometry with the P atoms in a trans arrangement, forming two five-membered chelate rings. Four intra-molecular C-H⋯O hydrogen bonds occur. The crystal packing reveals one weak inter-molecular C-H⋯O hydrogen bond, which self-assembles the mol-ecules into infinite chains parallel to the b axis.

Anion-π Interactions with Fluoroarenes.

Water and oxoanion encapsulation chemistry in a 1H-pyrazole azacryptand

Anion complexes of the cryptand built with the tripodal amine tris(2-aminoethyl)amine, known as tren, with water and several oxoanions of biological and environmental interest (nitrate, sulfate, phosphate, perchlorate and arsenate) have been crystallized from aqueous solution and resolved with single-crystal X-ray diffraction. All crystals show guest species encapsulated in the interior of the cavity as well as, in some cases, sitting in the grooves defined by the arms of the macrocycle. Hydrogen bonding and electrostatic interactions play a major role in anion binding to the host. The macrocycle is able to encapsulate anions in a wide range of protonation degrees. Solution studies have bee…

Combining organocatalysis and lanthanide catalysis: a sequential one-pot quadruple reaction sequence/hetero-Diels-Alder asymmetric synthesis of functionalized tricycles

A stereoselective one-pot synthesis of functionalized complex tricyclic polyethers has been achieved using the combination of secondary amine and lanthanide catalysis. This one-pot quadruple reaction/Hetero-Diels–Alder sequence gave good yields (per step) as well as excellent diastereo- and enantioselectivities. Furthermore, the particular combination of lanthanide complexes with organocatalysis is one of the first examples described for sequential catalysis.

Ein doppeltes Calix[4]aren in 1,3-alternate-Konformation

Cover Feature: Highly Enantioselective Kinetic Resolution of Michael Adducts through N-Heterocyclic Carbene Catalysis: An Efficient Asymmetric Route to Cyclohexenes (Chem. Eur. J. 39/2018)

Synthesis, characterization and crystal structure of the bimetallic cyano-bridged [(η5-C5H5)(PPh3)2Ru(μ-CN)Ru(PPh3)2(η5-C5H5)][PF6]

Abstract The bimetallic cyano-bridged [(η 5 -C 5 H 5 )(PPh 3 ) 2 Ru(μ-CN)Ru(PPh 3 ) 2 (η 5 -C 5 H 5 )][PF 6 ] ( 1 ) was prepared by reaction of [(η 5 -C 5 H 5 )(PPh 3 ) 2 RuCl] with N , N ′-bis(cyanomethyl)ethylenediamine. The single crystal structure determined by X-ray diffraction showed crystallization on the triclinic P1 space group with a perfect alignment of the cyanide bridges. This accentric crystallization was explored having in view the NLO properties at the macroscopic level, determined by the Kurtz Powder technique. Besides the very low efficiency values for the second harmonic generation, the value obtained for the bimetallic complex 1 showed to be higher than one of the parent…

Noncovalentπ⋅⋅⋅π-Stacked Exo-Functional Nanotubes: Subtle Control of Resorcinarene Self-Assembly

Complexation of enantiomerically pure tetraalkylammonium cations by ethyl resorcinarene

Molecular recognition via weak interactions of three enantiopure tetraalkylammonium cations 2–4 by ethyl resorcinarene 1 was studied in the solid state using single-crystal X-ray diffraction, in solution by proton nuclear magnetic resonance spectroscopy (1H NMR) titration and in the gas phase using electrospray ionisation mass spectrometry. The 1H NMR titration studies reveal the association constants for the 1:1 complexes to vary according to the size and electronic properties of the alkyl groups of the guest cations. In the solid state, the resorcinarene is deprotonated and the X-ray structure confirms the 1:1 complex 2+@1−  to be held together by multiple cation…π and C–H…π interactions.…

Ion pair complexes and anion binding in the solution of a ditopic receptor.

The synthesis and crystal structures with alkali halides of a ditopic benzo-15-crown-5 bis-urea receptor have been presented. In addition, the anion binding properties of and its alkali metal complexes in solution are presented. A comprehensive single-crystal X-ray crystallographic study of , all together 13 crystal structures, including the ion pair complexes with NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbF, RbCl, and RbI, give a detailed view of how behaves in the solid-state with different alkali halides depending on the size of the cation and anion. In the solid-state forms a 1 : 1 complex with a sodium cation and the anion is complexed as a contact (NaCl) or a separate ion pair (NaBr, NaI).…

Partial aminomethylation of resorcarenes.

Aminomethylation of resorcarenes at the wider rim with bulky diisopropylamine and formaline leads to trisubstituted derivatives. Analogous reaction with C(2v)-symmetrical resorcarene tetratosylate gives the monoaminomethylated compound. Further reactions of remaining unsubstituted resorcinol rings result in new resorcarene derivatives. [reaction: see text]

The new 5- or 6-azapyrimidine and cyanuric acid derivatives of L-ascorbic acid bearing the free C-5 hydroxy or C-4 amino group at the ethylenic spacer: CD-spectral absolute configuration determination and biological activity evaluations

Abstract We report on the synthesis of the novel types of cytosine and 5-azacytosine (1–9), uracil and 6-azauracil (13–18) and cyanuric acid (19–22) derivatives of l -ascorbic acid, and on their cytostatic activity evaluation in human malignant tumour cell lines vs. their cytotoxic effects on human normal fibroblasts (WI38). The CD spectra analysis revealed that cytosine (5 and 6), uracil (14–16), 6-azauracil (17) and cyanuric acid (21) derivatives of l -ascorbic acid bearing free amino group at ethylenic spacer existed as a racemic mixture of enantiomers, whereas L-ascorbic derivatives containing the C-5 substituted hydroxy group at the ethylenic spacer were obtained in (4R, 5S) enantiomer…

A “nucleophilic” iodine in a halogen-bonded iodonium complex manifests an unprecedented I+···Ag+ interaction

Summary When an electron is removed from a halogen atom, it forms a halenium ion X+ (X = I, Br, Cl). In halogen bonding (XB), X+ is considered as a strong XB donor, and when interacting with two XB acceptors (e.g., pyridine), it forms a halonium XB complex with a [N–I–N] three-center-four-electron bond with the two XB acceptors. An unprecedented I+···Ag+ interaction occurs between a [L1–I–L1]+ halogen-bonded complex and a [L2–Ag–L2]+ complex in which the iodonium ion acts like a nucleophile and donates electrons to the silver(I) cation. The X-ray diffraction analysis reveals a short contact [3.4608(3) A] between the I+ and Ag+ cations, and ITC measurements give a ΔG of −6.321 kcal/mol and K…

Synthesis, structure and reactivity of trans-UO22+ complexes of OH-containing ligands †

trans-Dioxouranium dinuclear complexes of a few OH-containing ligands possessing N-, O-binding sites were synthesized and characterised. Seven of these were also structurally characterised by single crystal X-ray diffraction. All these complexes exhibit symmetric U2O2 core structures in addition to having a seven-co-ordinated environment about each uranium centre. Even when the ligand possessed more than one CH2OH group, only one such group was found to be involved both in chelation as well as in bridging. These complexes exhibited facile transmetallation reactions with vanadium and molybdenum precursors. Though their core structures are alike, the complexes differ in their lattice arrangem…

X-ray analysis on the nanogram to microgram scale using porous complexes

X-ray single-crystal diffraction (SCD) analysis has the intrinsic limitation that the target molecules must be obtained as single crystals. Here we report a protocol for SCD analysis that does not require the crystallization of the sample. In our method, tiny crystals of porous complexes are soaked in a solution of the target, such that the complexes can absorb the target molecules. Crystallographic analysis clearly determines the absorbed guest structures along with the host frameworks. Because the SCD analysis is carried out on only one tiny crystal of the complex, the required sample mass is of the nanogram–microgram order. We demonstrate that as little as about 80 nanograms of a sample …

RETRACTED: trans-Tetrakis(pyridine)dichloroiron(II) as catalyst for Suzuki cross-coupling in ethanol and water

Aryl bromides can be coupled with phenylboronic acid in moderate to excellent yields using a transtetrakis(pyridine)dichloroiron(II) catalyst. The Suzuki–Miyaura reaction can be carried out under air in ethanol and aqueous ethanol with low catalyst loading. Addition of TBAB dramatically increases the yields in aqueous ethanol or in water. trans-Tetrakis(pyridine)dichloroiron(II) offers an environmental and less expensive method for the synthesis of biaryl compounds. This is the first example of an iron– pyridine catalyst for Suzuki cross-coupling.

Makrobicyclische Endorezeptoren: Synthese, Kristallstruktur und Einschluß organischer Gastmoleküle

Macrobicyclic Endoreceptors: Synthesis, Crystal Structure, and Inclusion of Organic Guests The macrobicyclic ligand 2 is synthesized in a one-step cyclization procedure. According to an X-ray structure analysis three dichloromethane guest molecules are included inside the cavity, whereas water and methanol are found outside the cavity. The rigid endo preorganization of the nitrogen donors allows the complexation of three 2,9-disubstituted 1,10-phenanthrolines inside the cavity.

Intra- vs Intermolecular Aurophilic Contacts in Dinuclear Gold(I) Compounds: Impact on the Population of the Triplet Excited State.

Two series of dinuclear gold(I) complexes that contain two Au–chromophore units (chromophore = dibenzofurane or dimethylfluorene) connected through a diphosphane bridge that differs in the flexibility and length (diphosphane = dppb for 1,4-bis(diphenylphosphino)butane, DPEphos for bis[(2-diphenylphosphino)phenyl]ether, xanthphos for 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and BiPheP for 2,2′-bis(diphenylphosphino)-1,1′-biphenyl) have been synthesized and structurally characterized. Their photophysical properties have been carefully investigated, paying attention to the role of the presence, or absence, of aurophilic contacts and their nature (intra- or intermolecular character). Th…

Binding of water and solvent molecules in a 25-membered-ring host compound

The macrocyclic 15- and 25-membered-ring pyridine oligomers 1 and 2 containing three and five methoxy substituents in the 4-position of the pyridine rings were prepared by Muller-Roscheisen cyclization and then isolated by chromatography. They are attractive as synthetic endobasic receptor molecules. X-ray structure analysis exhibits the inclusion of hydrogen-bonded solvent molecules (water and trichloromethane) inside the pentameric macrocycle 2.

Host-Guest Complexes of C-Ethyl-2-methylresorcinarene and Aromatic N,N′-Dioxides

The C‐ethyl‐2‐methylresorcinarene (1) forms 1:1 in‐cavity complexes with aromatic N,N′‐dioxides, only if each of the aromatic rings has an N−O group. The structurally different C‐shaped 2,2′‐bipyridine N,N′‐dioxide (2,2′‐BiPyNO) and the linear rod‐shaped 4,4′‐bipyridine N,N′‐dioxide (4,4′‐BiPyNO) both form 1:1 in‐cavity complexes with the host resorcinarene in C4v crown and C2v conformations, respectively. In the solid state, the host–guest interactions between the 1,3‐bis(4‐pyridyl)propane N,N′‐dioxide (BiPyPNO) and the host 1 stabilize the unfavorable anti‐gauche conformation. Contrary to the N,N′‐dioxide guests, the mono‐N‐oxide guest, 4‐phenylpyridine N‐oxide (4PhPyNO), does not form an…

Iron(III) Chloride as a Mild Catalyst for the Dearomatizing Cyclization of N-Acylindoles

A catalytic approach for the preparation of indolines by dearomatizing cyclization is presented. FeCl3 acts as a catalyst to afford tetracyclic 5a,6-dihydro-12H-indolo[2,1-b][1,3]benzoxazin-12-ones in good yields. The cyclization also proceeds with tosylamides forming C-N bonds in 53% yield.

Synthesis, characterization, and complexation of tetraarylborates with aromatic cations and their use in chemical sensors.

Five aromatic borate anions, namely tetrakis(4-phenoxyphenyl)borate (1), tetrakis(biphenyl)borate (2), tetrakis(2-naphthyl)borate (3), tetrakis(4-phenylphenol)borate (4), and tetrakis(4-phenoxy)borate (5), have been prepared and tested as ion-recognition sites in chemical sensors for certain aromatic cations and metal ions. To gain further insight into the complexation of the cations, some complexes have been prepared and structurally characterized. The complexation behavior of 1 and 2 towards N-methylpyridinium (6), 1-ethyl-4-(methoxycarbonyl)pyridinium (7), tropylium (8), imidazolium (9), and 1-methylimidazolium (10) cations has been studied, and the stability constants of the complexes o…

A Supramolecular Chiral Auxiliary Approach: “Remote Control ”of Stereochemistry at a Hierarchically Assembled Dimeric Helicate

Dimeric hierarchically-assembled titanium(IV) helicates are in solvent-dependent equilibrium with the corresponding monomers. Statistically formed mixtures of such complexes bearing chiral stereocontrolling ligands and achiral diene-substituted ligands show high diastereoselectivity and reasonable enantioselectivity in the Diels-Alder reaction with maleimides if the reaction proceeds with the dimer but not with the monomer. Thus, solvent dependent switching between the monomer and dimer enables on/off switching of the enantioselectivity.

Bis-urea macrocycles with a deep cavity

“Furlongelb” - ein 1,3-Dioxepin-Derivat

Asymmetric Synthesis of Functionalized Tricyclic Chromanes via an Organocatalytic Triple Domino Reaction

A highly stereoselective triple domino reaction for the synthesis of functionalized tricyclic chromane scaffolds has been developed. A secondary amine-catalyzed domino Michael/Michael/aldol condensation reaction between aliphatic aldehydes, nitro-chromenes, and α,β-unsaturated aldehydes leads to the formation of synthetically important tricyclic chromanes bearing four contiguous stereogenic centers including a tetrasubstituted carbon in good yields (20–66%) and excellent stereoselectivities (>20:1 dr and >99% ee).

Hexagonal Microparticles from Hierarchical Self-Organization of Chiral Trigonal Pd3L6 Macrotetracycles

Construction of structurally complex architectures using inherently chiral, asymmetric, or multi-heterotopic ligands is a major challenge in metallosupramolecular chemistry. Moreover, the hierarchical self-organization of such complexes is unique. Here, we introduce a water-soluble, facially amphiphilic, amphoteric, chiral, asymmetric, and hetero-tritopic ligand derived from natural bile acid, ursodeoxycholic acid. We show that via the supramolecular transmetalation reaction, using nitrates of Cu(II) or Fe(III), and subsequently Pd(II), a superchiral Pd3L6 complex can be obtained. Even though several possible constitutional isomers of Pd3L6 could be formed, because of the ligand asymmetry a…

Asymmetric Synthesis of Spirocyclic β-Lactams through Copper-Catalyzed Kinugasa/Michael Domino Reactions

The first copper-catalyzed highly chemo-, regio-, diastereo-, and enantioselective Kinugasa/Michael domino reaction for the desymmetrization of prochiral cyclohexadienones is described. In the presence of a chiral copper catalyst, alkyne-tethered cyclohexadienones couple with nitrones to generate the chiral spirocyclic lactams with excellent stereoselectivity (up to 97 % ee, >20:1 dr). The new method provides direct access to versatile highly functionalized spirocyclic β-lactams possessing four contiguous stereocenters, including one quaternary and one tetra-substituted stereocenter.

[2,6-Bis(di-tert-butylphosphinomethyl)phenyl-&amp;#954;3P,C1,P&amp;#8242;](trifluoroacetato)palladium(II)

The PdII atom in the title compound, [Pd(C2F3O2)(C24H43P2)], adopts a distorted square-planar geometry with the P atoms in a trans arrangement, forming two five-membered chelate rings. Four intramolecular C&amp;#8212;H...O hydrogen bonds occur. The crystal packing reveals one weak intermolecular C&amp;#8212;H...O hydrogen bond, which self-assembles the molecules into infinite chains parallel to the b axis.

[N⋅⋅⋅I+⋅⋅⋅N] Halogen-Bonded Dimeric Capsules from Tetrakis(3-pyridyl)ethylene Cavitands

Two [N⋅⋅⋅I+⋅⋅⋅N] halogen-bonded dimeric capsules using tetrakis(3-pyridyl)ethylene cavitands with different lower rim alkyl chains are synthesized and analyzed in solution and the gas phase. These first examples of symmetrical dimeric capsules making use of the iodonium ion (I+) as the main connecting module are characterized by 1H NMR spectroscopy, diffusion ordered NMR spectroscopy (DOSY), electrospray ionization mass spectrometry (ESI-MS), and ion mobility-mass spectrometry (TW-IMS) experiments. The synthesis and effective halogen-bonded dimerization proceeds through analogous dimeric capsules with [N⋅⋅⋅Ag+⋅⋅⋅N] binding motifs as the intermediates as evidenced by the X-ray structures of …

Chasing Weak Forces: Hierarchically Assembled Helicates as a Probe for the Evaluation of the Energetics of Weak Interactions.

London dispersion forces are the weakest interactions between molecules. Because of this, their influence on chemical processes is often low, but can definitely not be ignored, and even becomes important in cases of molecules with large contact surfaces. Hierarchically assembled dinuclear titanium(IV) helicates represent a rare example in which the direct observation of London dispersion forces is possible in solution even in the presence of strong cohesive solvent effects. Hereby, the dispersion forces do not unlimitedly support the formation of the dimeric complexes. Although they have some favorable enthalpic contribution to the dimerization of the monomeric complex units, large flexible…

1,2‐Benzothiazine Derivatives from Sulfonimidamides by Metal‐Catalyzed Annulation Reactions in Solution and under Solvent‐Free Mechanochemical Conditions

Advanced synthesis &amp; catalysis (2021). doi:10.1002/adsc.202001505 special issue: "Hot Topic: C-H Activation"

Glycosylamines of 4,6-O-butylidene-α-d-glucopyranose: synthesis and characterization of glycosylamines, and the crystal structure of 4,6-O-butylidene-N-(o-chlorophenyl)-β-d-glucopyranosylamine

A total of nine glycosylamines of 4,6-O-butylidene-α-D-glucopyranose were synthesized using primary amines having various groups in their ortho- or para-positions. Among these, six are monoglycosylamines, including one primary glycosylamine, and three are bis-glycosylamines. All these compounds were characterized by 1H, 1H–1H COSY, 1H–13C COSY and 13C NMR spectroscopy and FTIR spectra. The FAB mass spectra provided the molecular weights of the products by exhibiting the corresponding molecular ion peaks. The crystal structure of 4,6-O-butylidene-N-(o-chlorophenyl)-β-D-glucopyranosylamine revealed the C-1 glycosylation, the β-anomeric nature, and the 4C1 chair conformation of the saccharide …

Synthesis, structure and photophysical properties of a highly luminescent terpyridine-diphenylacetylene hybrid fluorophore and its metal complexes

A new fluorescent terpyridyl-diphenylacetylene hybrid fluorophore 4′-[4-{(4-methoxyphenyl)ethynyl}phenyl]-2,2′:6′,2′′-terpyridine, L, was synthesized via Sonogashira cross-coupling of 4′-(4-bromophenyl)-2,2′:6′,2′′-terpyridine and 4-ethynylanisole in the presence of Pd(PPh3)4/CuI as a catalyst. The solid state structure of L shows a trans arrangement of pyridine nitrogen atoms along the interannular bond in the terpyridine domain. Five transition metal complexes of L, {[FeL2](CF3SO3)2 (1), [ZnL2](ClO4)2 (2), [CdL2](ClO4)2 (3), [RuL2](PF6)2 (4), and PtMe3IL (5)}, have also been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. The X-ray crystal structu…

Frontispiece: Positive Allosteric Control of Guests Encapsulation by Metal Binding to Covalent Porphyrin Cages

Organocatalytic Enantioselective Vinylogous Henry Reaction of 3,5-Dimethyl-4-nitroisoxazole with Trifluoromethyl Ketones

The enantioselective vinylogous Henry reaction of 3,5-dimethyl-4-nitroisoxazole with trifluoromethyl ketones employing a bifunctional squaramide organocatalyst has been developed. A series of isoxazole bearing trifluoromethyl-substituted tertiary alcohols, 2-substituted (R)-1,1,1-trifluoro-3-(3-methyl-4-nitroisoxazol-5-yl)propan-2-ols, were obtained under these mild reaction conditions in good yields and moderate to good enantioselectivities

C–S bond cleavage by cobalt: synthesis, characterization and crystal structure determination of 1,2-di-(o-salicylaldiminophenylthio)ethane and its Co(III) product with C–S bond cleaved fragments

1,2-Di-(o-salicylaldiminophenylthio)ethane reacts with Co(II) salts to form a complex with oxidative cleavage of the C–S bond, to result in the formation of a Co(III) complex of the cleaved ligands.

Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution

A novel eight-membered macrocycle of the hemicucurbit[n]uril family, chiral (all-R)-cyclohexanohemicucurbit[8]uril (cycHC[8]) binds anions in a purely protic solvent with remarkable selectivity. The cycHC[8] portals open and close to fully encapsulate anions in a 1 : 1 ratio, resembling a molecular Pac-Man™. Comprehensive gas, solution and solid phase studies prove that the binding is governed by the size, shape and charge distribution of the bound anion. Gas phase studies show an order of SbF6− ≈ PF6− > ReO4− > ClO4− > SCN− > BF4− > HSO4− > CF3SO3− for anion complexation strength. An extensive crystallographic study reveals the preferred orientations of the anions within the octahedral cav…

Efficient stabilisation of a dihydrogenphosphate tetramer and a dihydrogenpyrophosphate dimer by a cyclic pseudopeptide containing 1,4-disubstituted 1,2,3-triazole moieties

A cyclic pseudooctapeptide 2 is described containing 1,4-disubstituted 1,2,3-triazole moieties. This compound features eight converging hydrogen bond donors along the ring, namely four amide NH and four triazole CH groups, which enable 2 to engage in interactions with anions. While fully deprotonated sulfate anions exhibit only moderate affinity for 2, protonated anions such as dihydrogenpyrophosphate and dihydrogenphosphate anions are strongly bound. Complexation of the phosphate-derived anions involves sandwiching of a dihydrogenpyrophosphate dimer or a dihydrogenphosphate tetramer between two pseudopeptide rings. X-ray crystallography provided structural information, while 1 H NMR spectr…

Selective Formation of S4- and T-Symmetric Supramolecular Tetrahedral Cages and Helicates in Polar Media Assembled via Cooperative Action of Coordination and Hydrogen-Bonds

We report on the synthesis and self-assembly study of novel supramolecular monomers encompassing quadruple hydrogen-bonding motifs and metal coordinating 2,2’-bipyridine units. When mixed with metal ions such as Fe2+ or Zn2+, the tetrahedron cage complexes are formed in quantitative yields and full diastereoselectivity, even in highly polar acetonitrile or methanol solvents. The symmetry of the complexes obtained has been shown to depend critically on the flexibility of the ligand. Restriction of the rotation of the hydrogen-bonding unit with respect to the metal coordinating site results in a T-symmetric cage, whereas by introducing flexibility either through a methylene linker or rotating…

Synthesis of Chlorinated Biphenyls by Suzuki Cross-Coupling Using Diamine or Diimine-Palladium Complexes

Several novel diimines (Salen-type ligands) 2a–2i and their reduced diamine counterparts 3b,3d–3g and 3i form complexes 4a–4i, 5b,5d–5g, and 5i with PdCl2 in DMF or methanol. Using 1 mol-% of the isolated complexes 4e and 5f many polychlorinated biphenyls (PCBs) can be prepared in moderate to excellent yields according to the Suzuki crosscoupling protocol with contact to air. Several 4-acetylbiphen

Aggregation versus Biological Activity in Gold(I) Complexes. An Unexplored Concept

The aggregation process of a series of mono- and dinuclear gold(I) complexes containing a 4-ethynylaniline ligand and a phosphane at the second coordination position (PR3-Au-C≡CC6H4-NH2, complexes 1-5, and (diphos)(Au-C≡CC6H4-NH2)2, complexes 6-8), whose biological activity was previously studied by us, has been carefully analyzed through absorption, emission, and NMR spectroscopy, together with dynamic light scattering and small-angle X-ray scattering. These experiments allow us to retrieve information about how the compounds enter the cells. It was observed that all compounds present aggregation in fresh solutions, before biological treatment, and thus they must be entering the cells as a…

Unexpected self-assembly of a homochiral metallosupramolecular M4L4 catenane

Two enantiomerically pure 9,9'-spirobifluorene-based bis(pyridine) ligands 1 and 2 were prepared to study their self-assembly behavior upon coordination to cis-protected palladium(II) ions. Whereas the sterically more demanding ligand, 2, gave rise to the expected dinuclear metallosupramolecular M2L2 rhombi, the sterically less demanding ligand, 1, acts as a template to give rise to a homochiral metallosupramolecular M4L4 catenane.

Poly(alkylidenimine) Dendrimers Functionalized with the Organometallic Moiety [Ru(η5-C5H5)(PPh3)2]+ as Promising Drugs Against Cisplatin-Resistant Cancer Cells and Human Mesenchymal Stem Cells

Here and for the first time, we show that the organometallic compound [Ru(&eta

Self-Organization of 2-Acylaminopyridines in the Solid State and in Solution

Aggregation of 2-acylaminopyridines and their 6-methyl derivatives in chloroform solution was studied by (1)H, (13)C, and (15)N NMR spectroscopies. The results were compared with (13)C and (15)N CPMAS NMR and IR spectral as well as with X-ray structural data. Intermolecular interactions in solution and in solid state were found to have a similar nature. Relatively strong N(amide)-H···N(pyridine) intermolecular hydrogen bonds enable dimerization to take place. Steric interactions in N-pivaloyl- and N-1-adamantylcarbonyl as well as that caused by the 6-methyl group hinder formation of the dimeric aggregates stabilized by the N(amide)-H···N(pyridine) intermolecular hydrogen bonds. In general, …

Asymmetric Synthesis of Spirocyclic β‐Lactams via Copper‐Catalyzed Kinugasa/Michael Domino Reactions

The first copper‐catalyzed highly chemo‐, regio‐, diastereo‐, and enantioselective Kinugasa/Michael domino reaction for the desymmetrization of prochiral cyclohexadienones is described. In the presence of a chiral copper catalyst, alkyne‐tethered cyclohexadienones couple with nitrones to generate the chiral spirocyclic lactams with excellent stereoselectivity (up to 97 % ee, >20:1 dr). The new method provides direct access to versatile highly functionalized spirocyclic β‐lactams possessing four contiguous stereocenters, including one quaternary and one tetra‐substituted stereocenter. peerReviewed

Heads or Tails? Sandwich-Type Metallocomplexes of Hexakis(2,3-di-O-methyl)-α-cyclodextrin

Native and synthetically modified cyclodextrins (CDs) are useful building blocks in construction of large coordination complexes and porous materials with various applications. Sandwich-type complexes (STCs) are one of the important groups in this area. Usually, coordination of secondary hydroxyls or the “head” portal of native CD molecules to a notional multinuclear ring of metal cations leads to formation of head-to-head STCs. Our study introduces a new CD-ligand, hexakis(2,3-di-O-methyl)-α-cyclodextrin, which enables formation of intriguing head-to-head, but also novel tail-to-tail STCs. Homometallic silver-based head-to-head STCs, AgPF6-STC and AgClO4-STC, were obtained by coordination …

The First Clamped and Strongly Deformed Adamantane

Selective recognition of neutral guests in an aqueous medium by a biomimetic calix[6]cryptamide receptor

The design of artificial receptors that can efficiently work in water is a challenging research area. A possible biomimetic approach for the elaboration of such receptors consists of associating a hydrophobic cavity with a polar polyfunctional binding site. On this basis, a hydrophilic calix[6]cryptamide decorated with oligo(ethylene glycol) units (i.e. 8) was synthesized through an efficient [1 + 1] macrocyclization reaction as the key-step. The complexation of neutral molecules was evaluated by NMR spectroscopy through competition experiments either in apolar or aqueous media. In both media, host 8 can bind neutral species that display H-bonding acceptor and donor groups such as amides or…

Redox-Responsive Host-Guest Chemistry of a Flexible Cage with Naphthalene Walls

“Naphthocage”, a naphthalene-based organic cage, reveals very strong binding (up to 1010 M–1) to aromatic (di)cationic guests, i.e., the tetrathiafulvalene mono- and dication and methyl viologen. Intercalation of the guests between two naphthalene walls is mediated by C–H···O, C–H···π, and cation···π interactions. The guests can be switched into and out of the cage by redox processes with high binding selectivity. Oxidation of the flexible cage itself in the absence of a guest leads to a stable radical cation with the oxidized naphthalene intercalated between and stabilized by the other two. Encapsulated guest cations are released from the cavity upon cage oxidation, paving the way to futur…

ESI-FTICR investigation of triethylammonium ion-driven resorcin[4]arene dimer formation and structure

In the course of mass spectrometric measurements a self-assembled hydrogen bonded resorcinarene dimer was observed, the formation of which was driven by the binding of triethylammonium ion as a guest and as an ionic label.

Porous 3D Printed Scavenger Filters for Selective Recovery of Precious Metals from Electronic Waste

Selective laser sintering (SLS) 3D printing is used to fabricate highly macroporous ion scavenger filters for recovery of Pd and Pt from electronic waste. The scavengers are printed by using a mixture of polypropylene with 10 wt% of type‐1 anion exchange resin. Porosities and the flow‐through properties of the filters are controlled by adjusting the SLS printing parameters. The cylinder‐shaped filters are used in selective recovery of Pd and Pt from acidic leachate of electronic waste simply by passing the solution through the object. Under such conditions, the scavenger filters are able to capture Pd and Pt as anionic complexes with high efficiency from a solution containing mixture of dif…

A magnetic look into the protecting layer of Au25 clusters

The field of molecular metal clusters protected by organothiolates is experiencing a very rapid growth. So far, however, a clear understanding of the fine interactions between the cluster core and the capping monolayer has remained elusive, despite the importance of the latter in interfacing the former to the surrounding medium. Here, we describe a very sensitive methodology that enables comprehensive assessment of these interactions. Pulse electron nuclear double resonance (ENDOR) was employed to study the interaction of the unpaired electron with the protons of the alkanethiolate ligands in four structurally related paramagnetic Au25(SR)0 18 clusters (R ¼ ethyl, propyl, butyl, 2-methylpro…

Hierarchical Ordering in Ternary Co-Crystals of C60, N-Benzyl Ammonium Resorcinarene Bromide and Solvent Molecules

Co-crystallization of C60 together with an N-benzyl ammonium resorcinarene bromide from toluene:1,2-dichloroethane mixture results in ternary co-crystals where the modulated C60 lattice entraps dimeric resorcinarene assemblies, which, in turn, have 149 and 280 A3 cavities filled with 1,2-dichloroethane molecules.

Front Cover: The Important Role of the Nuclearity, Rigidity, and Solubility of Phosphane Ligands in the Biological Activity of Gold(I) Complexes (Chem. Eur. J. 55/2018)

Cover Picture: An Unlockable-Relockable Iron Cage by Subcomponent Self-Assembly (Angew. Chem. Int. Ed. 43/2008)

2,3-Dihydro-1,2,6-thiadiazine 1-Oxides by Biginelli-Type Reactions with Sulfonimidamides under Mechanochemical Conditions.

Biginelli-type multicomponent reactions (MCRs) with NH-free sulfonimidamides provide 2,3-dihydro-1,2,6-thiadiazine 1-oxides in high yields. The couplings are performed in a planetary ball mill under solvent-free mechanochemical conditions. Acetic acid or ytterbium triflate are used as catalysts. A representative product was characterized by X-ray single crystal structure analysis revealing molecular details of the highly functionalized three-dimensional heterocycle. Further product modifications lead to additional structural scaffolds.

Expansion and Compression of a Helicate with Central Diol-Units as Stereocontrolling Moieties

The dicatechol ester ligand 2-H4 forms the compressed helicate Li4[(2)3Ti2] which upon removal of the internally bound lithium cations expands. In the compressed form, the chiral diol units control the stereochemistry of the complex which is lost upon expansion of the system. peerReviewed

Das erste verklammerte und stark deformierte Adamantan

N‐Heterocyclic Carbene Catalyzed Asymmetric Synthesis of Pentacyclic Spirooxindoles via [3+3] Annulations of Isatin‐Derived Enals and Cyclic N‐Sulfonyl Ketimines

Thermodynamically driven self-assembly of pyridinearene to hexameric capsules

Pyridinearene macrocycles have previously shown unique host–guest properties in their capsular dimers including endo complexation of neutral molecules and exo complexation of anions. Here, we demonstrate for the first time the formation of hydrogen bonded hexamer of tetraisobutyl-octahydroxypyridinearene in all three states of matter – gas phase, solution and solid-state. Cationic tris(bipyridine)ruthenium(II) template was found to stabilize the hexamer in gas phase, whereas solvent molecules do this in condensed phases. In solution, the capsular hexamer was found to be the thermodynamically favoured self-assembly product and transition from dimer to hexamer occurred in course of time. The …

Preparation of potentially porous, chiral organometallic materials through spontaneous resolution of pincer palladium conformers.

Understanding the mechanism by which advanced materials assemble is essential for the design of new materials with desired properties. Here, we report a method to form chiral, potentially porous materials through spontaneous resolution of conformers of a PCP pincer palladium complex ({2,6-bis[(di-t-butylphosphino)methyl]phenyl}palladium(II)halide). The crystallisation is controlled by weak hydrogen bonding giving rise to chiral qtz-nets and channel structures, as shown by 16 such crystal structures for X = Cl and Br with various solvents like pentane and bromobutane. The fourth ligand (in addition to the pincer ligand) on palladium plays a crucial role; the chloride and the bromide primaril…

Rigid biobased polycarbonates with good processability based on a spirocyclic diol derived from citric acid

Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bicyclic diketone (cis-bicyclo[3.3.0]octane-3,7-dione, obtained from citric acid) using trimethylolpropane. This spiro-diol monomer has two reactive primary hydroxyl groups and the synthesis from inexpensive biobased starting materials is straightforward and readily upscalable, involving no chromatographic purification. In order to explore the useful…

Repetitive‐Synthesis of Bulky Dendrimers – A Reversibly Photoactive Dendrimer with Six Azobenzene Side Chains

Dendrimers with bulky repeating units containing up to 43 benzene rings (in 9) have been obtained by using a repetitive divergent synthetic strategy (three generations). The new functional dendrimer 13 containing six azobenzene units at the periphery was synthesized allowing a reversible switching of the shape and size of the molecule upon irradiation. An X-ray structure analysis of the dendritic molecule 3a shows the inclusion of acetonitrile.

Positive Allosteric Control of Guests Encapsulation by Metal Binding to Covalent Porphyrin Cages

The allosteric control of the receptor properties of two flexible covalent cages is reported. These receptors consist of two zinc(II) porphyrins connected by four linkers of two different sizes, each incorporating two 1,2,3‐triazolyl ligands. Silver(I) ions act as effectors, responsible for an on/off encapsulation mechanism of neutral guest molecules. Binding silver(I) ions to the triazoles opens the cages and triggers the coordination of pyrazine or the encapsulation of N,N′‐dibutyl‐1,4,5,8‐naphthalene diimide. The X‐ray structure of the silver(I)‐complexed receptor with short connectors is reported, revealing the hollow structure with a cavity well‐defined by two eclipsed porphyrins. Rath…

Molecular Pacman: Folding, Inclusion, and X-ray Structures of Tri- and Tetraamino Piperazine Cyclophanes

Reaction of piperazine and 1,3-bis(bromomethyl)-2-nitrobenzene under high-dilution conditions yields cyclic trimeric trinitro, tetrameric tetranitro, and pentameric pentanitro piperazine cyclophanes. Reduction of the nitro groups with SnCl(2) under acidic conditions produces the corresponding triamino and tetraamino piperazine cyclophanes. The solution studies of both nitro and amino piperazine cyclophanes at 30 degrees C by (1)H NMR spectroscopy shows symmetrical structures owing to the fast conformational exchange, whereas the low temperature studies of the tetraamino piperazine cyclophane reveals interesting dynamic behavior that indicates additional intramolecular interactions. Careful …

N-Benzyl-2,3,4,5,6-pentafluorobenzamide

In the title compound, C14H8F5NO, the dihedral angle between the planes of the pentafluorophenyl and phenyl rings is 18.34&amp;#8197;(5)&amp;#176;. An intermolecular N&amp;#8212;H...O hydrogen bond between the amide groups connects these molecules to form an infinite chain through the crystal structure. One weak intermolecular C&amp;#8212;H...O contact and one &amp;#960;&amp;#8211;&amp;#960; interaction [centroid&amp;#8211;centroid distance = 3.772&amp;#8197;(3)&amp;#8197;&amp;#197;] are also involved in crystal structure stabilization between the phenyl rings.

[3]Rotaxanes and [3]pseudorotaxanes with a rigid two-bidentate chelate axle threaded through two coordinating rings

New [3]rotaxanes and [3]pseudorotaxanes have been synthesised using the “gathering and threading” effect of copper(I). By using click chemistry as the “stoppering” reaction, a good yield of the [3]rotaxane was obtained, either as a dicopper complex or as a metal-free compound after demetallation. The axle contains a central rigid aromatic block incorporating two bidentate chelates, and the threaded macrocycles are 30-membered rings. A model dicopper(I) [3]pseudorotaxane whose axle was end-functionalised by triisopropylsilyl groups could be crystallised and studied by X-ray diffraction. A particularly attractive structure was obtained showing a “slanted” geometry for the two rings and the ax…

Flying Capsules: Mass Spectrometric Detection of Pyrogallarene and Resorcinarene Hexamers

Synthesis, thermal properties and X-ray structural study of weak C–H⋯OC hydrogen bonding in aliphatic polyester dendrimers

Dendritic polyester compounds based on polyol with three, four and six reactive hydroxy groups as a molecular core, chloroacetyl chloride (or bromoacetyl bromide) and sodium metal enolate were prepared by a simple two-step synthetic procedure. The compounds were characterised by using the NMR and MS techniques, and the thermal properties were measured by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The structures of the crystalline compounds were determined by X-ray single crystal diffraction. Detailed analysis of the structures showed that the self-complementarity of the molecules together with a multitude of weak C-H⋯O=C hydrogen bonding results in crystal…

Encapsulation of Xenon by a Self-Assembled Fe4L6 Metallosupramolecular Cage

We report (129)Xe NMR experiments showing that a Fe4L6 metallosupramolecular cage can encapsulate xenon in water with a binding constant of 16 M(-1). The observations pave the way for exploiting metallosupramolecular cages as economical means to extract rare gases as well as (129)Xe NMR-based bio-, pH, and temperature sensors. Xe in the Fe4L6 cage has an unusual chemical shift downfield from free Xe in water. The exchange rate between the encapsulated and free Xe was determined to be about 10 Hz, potentially allowing signal amplification via chemical exchange saturation transfer. Computational treatment showed that dynamical effects of Xe motion as well as relativistic effects have signific…

Selective Extraction and Efficient Binding in a Protic Solvent of Contact Ion Triplets by Using a Thiourea-Based Bis-Calix[6]arene Receptor

We report a D3h-symmetric tail-to-tail bis-calix[6]thiourea 5 that displays two divergent cavities triply connected by thiourea linkages. This calix[6]tube was efficiently synthesized through a [1+1] macrocyclization reaction and characterized by X-ray diffraction analysis. The binding properties of this heterotritopic receptor were evaluated in a protic environment (i.e., CD3OD/CDCl3) through NMR studies. Thus, bis-calix[6]thiourea 5 exhibits a remarkable ability in the cooperative complexation of an anion sandwiched between two ammonium ions, a high selectivity for ammonium sulfate salts being observed. The anion is bound through multiple hydrogen-bonding interactions at the thiourea bind…

Recognition of Viologen Derivatives in Water by N-Alkyl Ammonium Resorcinarene Chlorides

Three water-soluble N-alkyl ammonium resorcinarene chlorides decorated with terminal hydroxyl groups at the lower rims were synthesized and characterized. The receptors were decorated at the upper rim with either terminal hydroxyl, rigid cyclohexyl, or flexible benzyl groups. The binding affinities of these receptors toward three viologen derivatives, two of which possess an acetylmethyl group attached to one of the pyridine nitrogens, in water were investigated via 1H NMR spectroscopy, fluorescence spectroscopy, and isothermal titration calorimetry (ITC). ITC quantification of the binding process gave association constants of up to 103 M–1. Analyses reveal a spontaneous binding process whi…

Synthesis of trifluoromethyl-substituted 1,2,6-thiadiazine 1-oxides from sulfonimidamides under mechanochemical conditions

TBS-protected or NH-sulfonimidamides react with β-alkoxyvinyl trifluoromethylketones under solvent-free mechanochemical conditions to give 3-trifluoromethyl-substituted three-dimensional 1,2,6-thiadiazine 1-oxides. C4-Functionalized products can be obtained by starting from cyclic enones and brominations of the initially formed heterocycles. The stability of the products was investigated by varying the pH value and storage under aerobic conditions.

Interaction Between Amines and N-Haloimides: a New Motif for Unprecedentedly Short Br...N and I...N Halogen Bonds

The complexes of N-bromosuccinimide or N-iodosuccinimide with a halogen bond acceptor, either 1,4-diazabicyclo[2.2.2]octane (DABCO), hexamethylenetetramine (HMTA) or 1,3,5-triazine (TRZ), led to an unprecedentedly strong (CO)2N–X⋯N halogen bond synthon (X = Br or I) determined from crystal structures of [DABCO]·[NBS]22, [HMTA]·[NBS]22, [TRZ]·[NIS]22 and [HMTA]·[NIS]44. The Br⋯N distances with DABCO and with HMTA donors were 2.347 A and 2.414 A being remarkably shorter (31% and 29%) than the sum of the VDW radii of nitrogen and bromide atoms, respectively. The corresponding I⋯N distances with HMTA and TRZ were 2.549 A and 2.596 A (27.8% and 26.4% less than the sum of the VDW radii of N and I…

Synthesis and characterization of new aromatic tweezers and complex formation with tropylium ion in 1,2-dichloroethane

A series of benzene and pyridine tweezers bearing phenyl, naphthyl and anthryl receptor units was prepared and characterized. The x-ray crystal structure of the 1,3-bis(9-methanolanthracene)methylbenzene ligand (5) is reported. UV–visible and NMR spectroscopy were used to investigate the host–guest chemistry of the new ligands in complexation with tropylium tetrafluoroborate as a model aromatic cationic guest in 1,2-dichloroethane. The appearance of coloured charge-transfer absorption bands demonstrates the complex formation with a tropylium ion. The enlargement of aryl receptor size from phenyl and naphthyl to anthryl increases the stability of complexes. Electron donor–acceptor interactio…

Self-Complementary Dimers of Oxalamide-Functionalized Resorcinarene Tetrabenzoxazines

Self‐complementarity is a useful concept in supramolecular chemistry, molecular biology and polymeric systems. Two resorcinarene tetrabenzoxazines decorated with four oxalamide groups were synthesized and characterized. The oxalamide groups possessed self‐complementary hydrogen bonding sites between the carbonyls and amide groups. The self‐complementary nature of the oxalamide groups resulted in self‐included dimeric assemblies. The hydrogen bonding interactions within the tetrabenzoxazines gave rise to the formation of dimers, which were confirmed by single‐crystal X‐ray diffractions analysis and supported by NMR spectroscopy and mass spectrometry. The self‐included dimers were connected b…

A coumarin based gold(i)-alkynyl complex: a new class of supramolecular hydrogelators.

A phosphine-gold(I)-alkynyl-coumarin complex, [Au{7-(prop-2-ine-1-yloxy)-1-benzopyran-2-one}(DAPTA)] (1), was synthesized and the formation of long luminescent fibers in solution was characterized via fluorescence microscopy and dynamic light scattering. The fibers presented strong blue and green luminescence, suggesting that the gold(I) in the complex increased intersystem crossing due to the heavy atom effect, resulting in a significant increase in triplet emission. The X-ray structure of the fibers indicates that both aurophilic, π–π interactions and hydrogen bonding contribute to their formation in aqueous solvents.

Redox-Responsive Host–Guest Chemistry of a Flexible Cage with Naphthalene Walls

"Naphthocage", a naphthalene-based organic cage, reveals very strong binding (up to 1010 M-1) to aromatic (di)cationic guests, i.e., the tetrathiafulvalene mono- and dication and methyl viologen. Intercalation of the guests between two naphthalene walls is mediated by C-H···O, C-H···π, and cation···π interactions. The guests can be switched into and out of the cage by redox processes with high binding selectivity. Oxidation of the flexible cage itself in the absence of a guest leads to a stable radical cation with the oxidized naphthalene intercalated between and stabilized by the other two. Encapsulated guest cations are released from the cavity upon cage oxidation, paving the way to futur…

Asymmetric Organocatalytic Synthesis of 4-Aminoisochromanones via a Direct One-Pot Intramolecular Mannich Reaction

Synthesis 48(24), 4451 - 4458(2016). doi:10.1055/s-0035-1562522

N-Heterocyclic Carbene Catalyzed Asymmetric Synthesis of Pentacyclic Spirooxindoles via [3+3] Annulations of Isatin-Derived Enals and Cyclic N-Sulfonyl Ketimines

A convenient enantioselective route to new types of pentacyclic spirooxindoles via [3+3] annulation reactions of isatin-derived enals and cyclic N-sulfonyl ketimines, using N-heterocyclic carbene (NHC) catalysis has been developed. The new protocol leads to pentacyclic spirooxindoles bearing a quaternary spirostereocenter in good yields and good to high enantiomeric ratios. peerReviewed

Macrocyclic (1,3)- and (1,4)-benzena-(1,4)-piperazinacyclophanes

New large, up to 45-membered macrocycles were synthesised from piperazine and m- and p-2,6-bis(bromomethyl)xylene under high dilution conditions. X-ray structures of compounds 3a, 4a, 5a, and 8b were determined. Surprisingly, none of the macrocycles prepared showed any inclusion properties towards small guest molecules. Instead, the compounds were found to self-organize during the packing process into larger structures due to the complementary of the molecular skeletons. In the crystalline state 3a forms nets, where the macrocycles are bound by HCH…N interactions to each other. 4a exits in a dimeric structure, which, in turn, further extends to a sheet structure. The positively charged phan…

Carbonyl Hypoiodites as Extremely Strong Halogen Bond Donors

Abstract Neutral halogen‐bonded O−I−N complexes were prepared from in situ formed carbonyl hypoiodites and aromatic organic bases. The carbonyl hypoiodites have a strongly polarized iodine atom with larger σ‐holes than any known uncharged halogen bond donor. Modulating the Lewis basicity of the selected pyridine derivatives and carboxylates leads to halogen‐bonded complexes where the classical O−I⋅⋅⋅N halogen bond transforms more into a halogen‐bonded COO−⋅⋅⋅I−N+ ion‐pair (salt) with an asymmetric O−I−N moiety. X‐ray analyses, NMR studies, and calculations reveal the halogen bonding geometries of the carbonyl hypoiodite‐based O−I−N complexes, confirming that in the solid‐state the iodine at…

Ti(iv)-amino triphenolate complexes as effective catalysts for sulfoxidation

C 3 -symmetric Ti (IV) amino triphenolate complexes efficiently catalyze, without previous activation and in excellent yields, the oxidation of sulfides at room temperature, using both CHP and the more environment friendly aqueous hydrogen peroxide as terminal oxidants, with catalyst loadings down to 0.01%. The Ti(IV) catalysts and the intermediate Ti(IV)-peroxo complexes have been characterized in solution by 1H NMR and ESI-MS techniques and via density functional studies.

Synthesis and Topological Determination of Hexakis-Substituted 1,4-Ditritylbenzene and Nonakis-Substituted 1,3,5-Tritritylbenzene Derivatives: Building Blocks for Higher Supramolecular Assemblies

Based on trityl moieties, novel organic building blocks have been prepared and structurally investigated. Substituted hexaphenyl-p-xylene (1,4-ditritylbenzene) as well as extended analogues thereof were prepared. Furthermore, a new family based on a 1,3,5-tritritylbenzene motif, connecting three trityl groups through a formal mesitylene unit, was developed. Both families were further converted through six- and nine-fold substitution reactions, respectively, to yield potent molecular building blocks for supramolecular assemblies.

Candida antarctica Lipase A-Based Enantiorecognition of a Highly Strained 4-Dibenzocyclooctynol (DIBO) Used for PET Imaging

The enantiomers of aromatic 4-dibenzocyclooctynol (DIBO), used for radiolabeling and subsequent conjugation of biomolecules to form radioligands for positron emission tomography (PET), were separated by kinetic resolution using lipase A from Candida antarctica (CAL-A). In optimized conditions, (R)-DIBO [(R)-1, ee 95%] and its acetylated (S)-ester [(S)-2, ee 96%] were isolated. In silico docking results explained the ability of CAL-A to differentiate the enantiomers of DIBO and to accommodate various acyl donors. Anhydrous MgCl2 was used for binding water from the reaction medium and, thus, for obtaining higher conversion by preventing hydrolysis of the product (S)-2 into the starting materi…

Asymmetric Synthesis of Spirobenzazepinones with Atroposelectivity and Spiro-1,2-Diazepinones by NHC-Catalyzed [3+4] Annulation Reactions

A strategy for the NHC-catalyzed asymmetric synthesis of spirobenzazepinones, spiro-1,2-diazepinones, and spiro-1,2-oxazepinones has been developed via [3+4]-cycloaddition reactions of isatin-derived enals (3C component) with in-situ-generated aza-o-quinone methides, azoalkenes, and nitrosoalkenes (4atom components). The [3+4] annulation strategy leads to the seven-membered target spiro heterocycles bearing an oxindole moiety in high yields and excellent enantioselectivities with a wide variety of substrates. Notably, the benzazepinone synthesis is atroposelective and an all-carbon spiro stereocenter is generated.

Perfluoro-1,1′-biphenyl and perfluoronaphthalene and their derivatives as π-acceptors for anions

Addition of anions to perfluorinated 1,1′-biphenyl 1 or naphthalene 2 results in a shift of the 19F NMR signals. However, any specific interaction cannot be assigned to this effect. In order to study the interaction in more detail, the salt derivatives 3 and 4 were prepared and studied by single crystal X-ray diffraction revealing weak anion–π interactions in the solid state.

Efficient Conversion of Light to Chemical Energy : Directional, Chiral Photoswitches with Very High Quantum Yields

Abstract Photochromic systems have been used to achieve a number of engineering functions such as light energy conversion, molecular motors, pumps, actuators, and sensors. Key to practical applications is a high efficiency in the conversion of light to chemical energy, a rigid structure for the transmission of force to the environment, and directed motion during isomerization. We present a novel type of photochromic system (diindane diazocines) that converts visible light with an efficiency of 18 % to chemical energy. Quantum yields are exceptionally high with >70 % for the cis–trans isomerization and 90 % for the back‐reaction and thus higher than the biochemical system rhodopsin (64 %). T…

Gold Nanowired: A Linear (Au25)n Polymer from Au25 Molecular Clusters

Au25(SR)18 has provided fundamental insights into the properties of clusters protected by monolayers of thiolated ligands (SR). Because of its ultrasmall core, 1 nm, Au25(SR)18 displays molecular behavior. We prepared a Au25 cluster capped by n-butanethiolates (SBu), obtained its structure by single-crystal X-ray crystallography, and studied its properties both experimentally and theoretically. Whereas in solution Au25(SBu)18(0) is a paramagnetic molecule, in the crystal it becomes a linear polymer of Au25 clusters connected via single Au-Au bonds and stabilized by proper orientation of clusters and interdigitation of ligands. At low temperature, [Au25(SBu)18(0)]n has a nonmagnetic ground s…

Zur Reaktion von ?Pyrazolonblau? mit Diazomethan

About the Reaction of „Pyrazolone Blue” with Diazomethane The reaction of “pyrazolone blue” with diazomethane was investigated. A pyridazinone derivative 3, a heterocyclic spiro-cyclopropyl product 4 and a compound 7, which contains three pyrazolone and two diazomethane entities, are formed. 3 reacts with an excess of diazomethane to the methoxy derivative 6. The spiro-cyclopropyl compound 4 is not stable and isomerizes to the corresponding 4,4′-methylidene-bispyrazolone 5. The structures of the products were established by spectroscopic methods and X-ray analysis.

New indications for the potential involvement of C–F-bonds in hydrogen bonding

Abstract Solid state structures of a selection of 2-fluoro-2-phenylcyclopropane derivatives were examined by X-ray crystallography in order to identify short intermolecular contacts of C–F groups to H–X moieties (X=C, N). Particularly, several cis -configured fluorinated phenylcyclopropane derivatives showed extremely close intermolecular contacts. The shortest of such C–H⋯F–C-distances (2.17 A, C–F–H angle 162°) was found in (1 S ,2 R )-(2-fluoro-2-phenylcyclopropyl)methyl N -(4-bromophenyl)carbamate ( 8 ) and the closest N–H⋯F–C-interaction (2.01 A, C–F–H angle 167°) was found in (±)- cis -2-fluoro-2-phenylcyclopropyl carboxamide ( 4 ). Comparison of the structures of several of the fluor…

Prenylated Flavonoids from the Roots of Tephrosia rhodesica

Five new compounds—rhodimer (1), rhodiflavan A (2), rhodiflavan B (3), rhodiflavan C (4), and rhodacarpin (5)—along with 16 known secondary metabolites, were isolated from the CH2Cl2–CH3OH (1:1) extract of the roots of Tephrosia rhodesica. They were identified by NMR spectroscopic, mass spectrometric, X-ray crystallographic, and ECD spectroscopic analyses. The crude extract and the isolated compounds 2–5, 9, 15, and 21 showed activity (100% at 10 μg and IC50 = 5–15 μM) against the chloroquine-sensitive (3D7) strain of Plasmodium falciparum. peerReviewed

Asymmetric Synthesis of Spiro-oxindole-ε-lactones through N-Heterocyclic Carbene Catalysis

An unprecedented N-heterocyclic carbene-catalyzed annulation of isatin-derived enals and o-hydroxyphenyl-substituted p-quinone methides as bifunctional reagents has been discovered. The new protocol involves a 1,6-addition of the homoenolate equivalent intermediates to the hydroxy donor-1,6-Michael acceptors and leads to spirocyclic oxindole-ε-lactones in high yields and very good stereoselectivities.

Synthesis, characterization and thermal properties of new aromatic quaternary ammonium bromides

Series of new aromatic R 2R′ 2N +Br - (R=benzyl, 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl; R′=ethyl, methyl, isopropyl) or RR′ 2NH +Br --type (R=benzyl, R′=isopropyl) quaternary ammonium bromides were prepared by using novel synthetic route in which a formamide (N,N-diethylformamide, N,N-dimethylformamide, N,N-diisopropylformamide) is treated with aralkyl halide in presence of a weak base. The compounds were characterized by 1H-NMR and 13C-NMR spectroscopy and mass spectrometry. Structures of the crystalline compounds were determined by X-ray single crystal diffraction, and in addition the powder diffraction method was used to study the structural similarities between the single crysta…

Very strong −N–X+⋯−O–N+ halogen bonds

A new (-)N-X(+)(-)O-N(+) paradigm for halogen bonding is established by using an oxygen atom as an unusual halogen bond acceptor. The strategy yielded extremely strong halogen bonded complexes with very high association constants characterized in either CDCl3 or acetone-d6 solution by (1)H NMR titrations and in the solid-state by single crystal X-ray analysis. The obtained halogen bond interactions, RXB, in the solid-state are found to be in the order of strong hydrogen bonds, viz. RXB ≈ RHB.

Dimeric iodine(i) and silver(i) cages from tripodal N-donor ligands via the [N–Ag–N]+ to [N–I–N]+ cation exchange reaction

The directionality of the [N–I–N]+ halogen bond makes iodine(I) ions impeccable tools in the design and construction of [N–I–N]+ halogen-bonded assemblies. The synthesis of dimeric iodine(I) cages with imidazole-derived N-donor tripodal ligands is described, as well as their corresponding silver(I) precursors. The addition of elemental iodine to the parent two-coordinate Ag(I) complexes produces iodine(I) complexes with three-center four-electron (3c–4e) [N–I–N]+ bonds. Complex formation via this cation exchange was confirmed by 1H and 1H–15N HMBC NMR studies in solution, and additionally by electrospray ionisation and ion mobility mass spectrometry analysis (MS) in the gas phase. The struc…

Homocalixpyridines: Ligands Exhibiting High Selectivity in Extraction and Sensor Processes

A novel spherical host architecture, based on pyridine subunits, has been created. It exhibits selective complexing properties toward soft metal ions (right), which have been tested in extraction and sensor processes. The complex-forming behaviour can be tailored by variation of the size of the cavity and by substitution. Homocalixpyridines are interesting in view of their application as selective carriers in separation and sensing techniques.

Halogen-Bonded Co-Crystals of Aromatic N-oxides : Polydentate Acceptors for Halogen and Hydrogen Bonds

The C-ethyl-2-methylresorcinarene (1) forms 1:1 in-cavity complexes with aromatic N,N′-dioxides, only if each of the aromatic rings has an N−O group. The structurally different C-shaped 2,2′-bipyridine N,N′-dioxide (2,2′-BiPyNO) and the linear rod-shaped 4,4′-bipyridine N,N′-dioxide (4,4′-BiPyNO) both form 1:1 in-cavity complexes with the host resorcinarene in C4v crown and C2v conformations, respectively. In the solid state, the host–guest interactions between the 1,3-bis(4-pyridyl)propane N,N′-dioxide (BiPyPNO) and the host 1 stabilize the unfavorable anti-gauche conformation. Contrary to the N,N′-dioxide guests, the mono-N-oxide guest, 4-phenylpyridine N-oxide (4PhPyNO), does not form an…

Chelate Cooperativity and Spacer Length Effects on the Assembly Thermodynamics and Kinetics of Divalent Pseudorotaxanes

Homo- and heterodivalent crown-ammonium pseudorotaxanes with different spacers connecting the two axle ammonium binding sites have been synthesized and characterized by NMR spectroscopy and ESI mass spectrometry. The homodivalent pseudorotaxanes are investigated with respect to the thermodynamics of divalent binding and to chelate cooperativity. The shortest spacer exhibits a chelate cooperativity much stronger than that of the longer spacers. On the basis of crystal structure, this can be explained by a noninnocent spacer, which contributes to the binding strength in addition to the two binding sites. Already very subtle changes in the spacer length, i.e., the introduction of an additional…

The Reaction Mechanism of Spirocylization and Stereoselectivity Studies for the Calyculin C16 -C25 Fragment

The mechanism of the double intramolecular hetero-Michael addition, a key reaction in the planned synthesis of the natural product calyculin C, has been studied by NMR. The cyclization follows Baldwin’s rules and proceeds first through a six-membered ring closure (6-endo-dig), followed by a five-membered ring cyclization (5-exo-trig). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Stereocontrolledα-Alkylation of Fully ProtectedL-Serine

Diastereoselective alkylation of the (2S,4S) and (2R,4S) diastereomers of 3-tert-butyl 4-methyl 2-tert-butyl-1,3-oxazolidine-3,4-dicarboxylate (1a/b) is reported. Formation of both diastereomers of these oxazolidines was achieved by changing the order of protection steps, and their relative and absolute configurations were determined by NOESY spectroscopy. The use of the bulky ring substituent tBu together with Boc as the N-protecting group led to the exclusive formation of only one alkylated diastereomer. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Dimerization of (+)-Lysergic Acid Esters

Dimer isomer mixtures, characterized by a bridgehead C8-C8' bond, (6a-7a; 6b-7b) were obtained from (+)-lysergic acid methyl or ethyl ester (1b; 1c) in a solution of methanol or ethanol. The isomers were separated, and their structures were determined by detailed NMR measurements and X-ray analysis. Density functional theory was applied to provide insight into the reaction mechanism. Based on an extended examination and the theoretical calculations, a plausible reaction sequence leading to dimers is also presented. The proposed mechanism has been verified by detecting the formation of the superoxide radical anion (O 2 * -).

Fluorescence enhancement of quinolines by protonation.

A study of the fluorescence enhancement of isoquinoline, acridine (benzo[b]quinoline) and benzo[h]quinoline is reported with six organic acids of different pKa values. Protonation was found to be an effective tool in the fluorescence enhancement of quinolines. A significant increase in the fluorescence intensity is observed only when strong acids are used, resulting in an over 50-fold increase in fluorescence with trifluoroacetic or benzenesulfonic acid and isoquinoline in a 1.5 : 1 ratio. The benzenesulfonic acid was found to be the most effective in the protonation of the bases despite its higher pKa value compared to trifluoro- and trichloroacetic acid. The X-ray crystal structures of 14…

From One-Pot NH-Sulfoximidations of Thiophene Derivatives to Dithienylethene-Type Photoswitches

Thiophene NH-sulfoximines have been synthesized using a one-pot NH-sulfoximidation reaction of thiophenes. The reactivity of the products was investigated, and the developed protocols were used for the synthesis of a new class of dithienylethene-type photoswitches containing a sulfoximidoyl group.

Halogen-bonded solvates of tetrahaloethynyl cavitands

The formation and structures of halogen-bonded solvates of three different tetrahaloethynyl cavitands with acetone, chloroform, acetonitrile, DMF and DMSO were prepared and investigated. The inclusion and host–guest behaviour of the resorcinarene cavitands was found to be highly dependent on the flexibility of the ethylene-bridging unit.

Design and synthesis of the first triply twisted Möbius annulene.

As long as 50 years ago theoretical calculations predicted that Mobius annulenes with only one π surface and one edge would exhibit peculiar electronic properties and violate the Huckel rules. Numerous synthetic attempts notwithstanding, the first singly twisted Mobius annulene was not prepared until 2003. Here we present a general, rational strategy to synthesize triply or even more highly twisted cyclic π systems. We apply this strategy to the preparation of a triply twisted [24]dehydroannulene, the structure of which was confirmed by X-ray analysis. Our strategy is based on the topological transformation of 'twist' into 'writhe'. The advantage is twofold: the product exhibits a lower deg…

Differential detection and quantification of cyclic AMP and other adenosine phosphates in live cell

A new naphthol-based rhodamine derivative (NpRD) has been developed for the selective and differential detection of adenosine 3′,5′-cyclic monophosphate (cAMP) and adenosine phosphates (APs) (ATP, ADP, and AMP) from other nucleotides. The simple detection and quantification of cAMP in human blood cells and in other samples based on the ‘turn on’ fluorescence properties of this chemosensor through colorimetry or fluorometry makes it unique for probable application in high throughput screening. peerReviewed

Hydrogen-Bonding Effects in Calix[4]arene Capsules

The synthesis and spectroscopic characterization of self-assembling calix[4]arene based capsules 1a.1a and 1b.1b are described. These compounds feature four urea substituents at the upper rims and four secondary amide fragments at the lower rims that can participate in inter- and intramolecular hydrogen bonding in apolar solution. Communication between the calixarene rims in 1a, b influences the self-assembled cavity's size and shape. Specifically. dimerization results in a perfect cone conformation of the calixarene skeleton in 1a, b and stabilizes a seam of intramolecular amide C=O...H-N hydrogen bonds at the lower rim. This seam is cycloenantiomeric, with either clockwise or counterclock…

The “nitrogen effect” : Complexation with macrocycles potentiates fused heterocycles to form halogen bonds in competitive solvents

Weak intermolecular forces are typically very difficult to observe in highly competitive polar protic solvents as they are overwhelmed by the quantity of competing solvent. This is even more challenging for three-component ternary assemblies of pure organic compounds. In this work, we overcome these complications by leveraging the binding of fused aromatic N-heterocycles in an open resorcinarene cavity to template the formation of a three-component halogen-bonded ternary assembly in a protic polar solvent system. peerReviewed

N‐Heterocyclic Carbene Catalyzed Quadruple Domino Reactions: Asymmetric Synthesis of Cyclopenta[ c ]chromenones

An N-heterocyclic carbene catalyzed domino sequence via α,β-unsaturated acyl azolium intermediates has been developed. This strategy provides a convenient enantioselective route to functionalized tricyclic coumarin derivatives and cyclopentanes. DFT studies and control experiments were performed to gain better insight into the reaction mechanism.

Self-assembly of a M4L6 complex with unexpected S4 symmetry

In a one-pot reaction 1,4-diaminobenzene and 2-formylpyridine, as the reacting subcomponents, self-assemble to a small supramolecular M4L6 pseudo-tetrahedron with unexpected S4 symmetry in the presence of Fe(ii) ions.

Back Cover: Water Structure Recovery in Chaotropic Anion Recognition: High-Affinity Binding of Dodecaborate Clusters to γ-Cyclodextrin (Angew. Chem. Int. Ed. 23/2015)

Bamboo-like Chained Cavities and Other Halogen-Bonded Complexes from Tetrahaloethynyl Cavitands with Simple Ditopic Halogen Bond Acceptors

Halogen bonding provides a useful complement to hydrogen bonding and metal-coordination as a tool for organizing supramolecular systems. Resorcinarenes, tetrameric bowl-shaped cavitands, have been previously shown to function as efficient scaffolds for generating dimeric capsules in both solution and solid-phase, and complicated one-, two-, and three-dimensional frameworks in the solid phase. Tetrahaloethynyl resorcinarenes (bromide and iodide) position the halogen atoms in a very promising “crown-like” orientation for acting as organizing halogen-bond donors to help build capsules and higher-order networks. Symmetric divalent halogen bond acceptors including bipyridines, 1,4-dioxane, and 1…

Polymorphic chiral squaraine crystallites in textured thin films

Chirality 32(5), 619 - 631 (2020). doi:10.1002/chir.23213

Unveiling Electronic Transitions in Three Novel Chiral Azo-Compounds Using Linear and Nonlinear Circular Dichroism: A Theoretical−Experimental Study

Herein, we report on the experimental and theoretically study of the linear absorption, electronic circular dichroism (ECD) spectra, as well as the two-photon absorption circular-linear dichroism measurements of three different chiral azo derivatives in dimethylsulfoxide solution. Using potential energy surfaces and frontier orbital analysis, we established the most stable conformation for each molecule and elucidated their different electronic transitions. Our theoretical calculations allowed us to unambiguously identify the spectral position of such transitions and correlate them with the spectral profiles observed in the two-photon absorption spectra. To further elucidate the characteris…

Complexation of planar, organic, five-membered cations with crown ethers

Complexation of six aromatic, nitrogen-containing cations with various crown ethers has been studied using 1H NMR, mass spectrometric and crystallographic methods. Hydrogen bonding appears to be the most important interaction in complexation, but minor effects such as π-stacking or cation–π interactions have also been observed. The stability constants of five different imidazolium perchlorate ·crown ether complexes and five other similar cation·DB18C6 complexes were determined by 1H NMR titration in acetonitrile solution. The stability of these complexes in solution and in the gas phase is discussed. The crystal structures of seven complexes were determined in order to study complexation in…

A linear open-chain piperazine-pyridine ligand and its meso-helical Co complex

Abstract An oligomeric ligand (HPPy) 2 P, N , N ′-bis[2-(6-( N -( N ′-(2-hydroxyethyl)piperazinyl)methyl)]piperazine, was designed to resemble structurally open-chain aza-crowns. Owing to the all- trans configuration of piperazine and pyridine free electron pairs, it should adopt a near linear overall structure in solvent. Theoretical calculations at ab initio level confirm the overall linear structure of free ligand. The crystal structure of the complex [(HPPy) 2 P][Co(NO 3 ) 2 ] 2 shows a contraction from ∼3 to 2 nm structure. Each coordination site creates either a Δ or Δ configuration around the metal ion, thus causing a ligand with an even number of coordination centres to be meso -hel…

Regioselective acylation of aminoresorcinarenes

Abstract The acid catalyzed hydrolytic cleavage of the oxazine rings in the readily available tetraoxazine derivatives of resorcinarenes results in tetraaminoresorcinarenes. A similar process applied to C2-symmetrical bisoxazine resorcinarene tetratosylates affords C2v-symmetrical resorcinarenediamines. The mild acylation of these resorcinareneamines with BOC-anhydride or para-nitrophenyl ester proceeds selectively at the nitrogen atoms without affecting the hydroxyl groups. Most of the resulting resorcinareneamides are thus obtained in preparative yields and can be easily purified by simple crystallizations. In the crystalline state the compounds obtained are found to bind chloride anions …

A novel caryophyllene type sesquiterpene lactone from Asparagus falcatus (Linn.); Structure elucidation and anti-angiogenic activity on HUVECs

Abstract In this study the novel caryophyllene type sesquiterpene lactone (aspfalcolide) has been isolated from the leaves of Asparagus falcatus (Linn.) and characterized by IR, 1D NMR, 2D NMR, EI–MS, HR–ESI–MS and X-ray single crystal diffraction analysis. The aspfalcolide crystallizes in the orthorhombic space group P212121 with a = 6.37360(10), b = 7.6890(2), c = 27.3281(6) A, α = β = γ = 90° and Z = 4. One intermolecular O–H⋯O hydrogen bond enforces these natural molecules to form infinite chains through the crystal. Aspfalcolide was screened for its anti-angiogenic activity in human umbilical vein endothelial cells (HUVECs) and the result showed the remarkable inhibitory effect of aspf…

Resolution and Determination of the Absolute Configuration of a Twisted Bis-Lactam Analogue of Tröger's Base: A Comparative Spectroscopic and Computational Study.

The first reported twisted bis-lactam, a racemic Tröger's base (TB) analogue (2), was resolved into its enantiomers on a chiral stationary phase HPLC column. The absolute configuration of (+)-2 was determined to be (R,R)-2 by comparing experimental and calculated vibrational circular dichroism (VCD) and electronic circular dichroism (ECD) spectra. The absolute configuration of (-)-2 was determined by comparing experimental and calculated electronic circular dichroism (ECD) spectra. The corresponding theoretical spectra were calculated using the lowest energy conformation of (R,R)-2 and (S,S)-2 at the B3LYP/6-31G(d,p) level of theory. The absolute configuration of (+)-2 was also determined t…

Enantioselective synthesis of pyrazolone α-aminonitrile derivatives via an organocatalytic Strecker reaction

A new organocatalytic enantioselective Strecker reaction of pyrazolone-derived ketimine electrophiles has been developed. Using pseudo-enantiomeric squaramide catalysts the nucleophilic 1,2-addition of trimethylsilyl cyanide to the ketimines efficiently provides a direct entry to both enantiomers of pyrazolone α- aminonitrile derivatives at will in good yields and high enantioselectivities for a wide variety of substrates. peerReviewed

Recognition and sensing of fluoride anion.

Fluoride anion recognition is attracting a mounting interest in the scientific community due to its duplicitous nature. It is a useful chemical for many industrial applications, and it has been used in human diet, but, recently it has been accused for several human pathologies. Here we describe the ample panorama of different approaches the chemists world-wide have employed to face the challenge of fluoride binding, and we outline some of the research which in our view can contribute to the development of this field, especially when fluoride binding has to be achieved in highly competitive protic solvents and water.

Biocompatible Hydrogelators Based on Bile Acid Ethyl Amides

Four novel bile acid ethyl amides were synthetized using a well-known method. All the four compounds were characterized by IR, SEM, and X-ray crystal analyses. In addition, the cytotoxicity of the compounds was tested. Two of the prepared compounds formed organogels. Lithocholic acid derivative 1 formed hydrogels as 1% and 2% (w/v) in four different aqueous solutions. This is very intriguing regarding possible uses in biomedicine. peerReviewed

Molecular aggregation in selected crystalline 1:1 complexes of hydrophobicD- andL-amino acids. IV. TheL-phenylalanine series

The amino acid L-phenylalanine has been cocrystallized with D-2-aminobutyric acid, C(9)H(11)NO(2).C(4)H(9)NO(2), D-norvaline, C(9)H(11)NO(2).C(5)H(11)NO(2), and D-methionine, C(9)H(11)NO(2).C(5)H(11)NO(2)S, with linear side chains, as well as with D-leucine, C(9)H(11)NO(2).C(6)H(13)NO(2), D-isoleucine, C(9)H(11)NO(2).C(6)H(13)NO(2), and D-allo-isoleucine, C(9)H(11)NO(2).C(6)H(13)NO(2), with branched side chains. The structures of these 1:1 complexes fall into two classes based on the observed hydrogen-bonding pattern. From a comparison with other L:D complexes involving hydrophobic amino acids and regular racemates, it is shown that the structure-directing properties of phenylalanine closel…

Cooperativity of H-bonding and anion–π interaction in the binding of anions with neutral π-acceptors

A rare anion-π complex between bromide and a neutral receptor is reported and related receptor systems are studied with a series of anions. The interaction is observed in the solid state and in solution, and further evidence for it is obtained by a computational study.

Iodine(i) complexes incorporating sterically bulky 2-substituted pyridines

The silver(I) and iodine(I) complexes of the 2-substituted pyridines 2-(diphenylmethyl)pyridine (1) and 2-(1,1-diphenylethyl)pyridine (2), along with their potential protonated side products, were synthesised to investigate the steric limitations of iodine(I) complex formation. The complexes were characterised by 1H and 1H–15N HMBC NMR, X-ray crystallography, and DFT calculations. The solid-state structures for the silver(I) and iodine(I) complexes were extensively compared to the literature and analysed by DFT to examine the influence of the sterically bulky pyridines and their anions. peerReviewed

Strong N−X···O−N Halogen Bonds: Comprehensive Study on N‐Halosaccharin Pyridine N‐oxide Complexes

A detailed study of the strong N−X⋯−O−N+ (X = I, Br) halogen bonding interactions in solution and in the solid‐state reports 2×27 donor×acceptor complexes of N‐halosaccharins and pyridine N‐oxides (PyNO). Density Functional Theory (DFT) calculations were used to investigate the X···O halogen bond (XB) interaction energies in 54 complexes. The XB interaction energies were found to vary from –47.5 to –120.3 kJ mol–1, with the strongest N−I⋯−O−N+ XBs approaching those of 3‐center‐4‐electron [N–I–N]+ halogen‐bonded systems (∼160 kJ mol–1). Using a subset of 32 complexes, stabilized only through N−X···−O−N+ XB interactions, a simplified, computationally fast, electrostatic model to predict the X…

Synthesis, characterization and thermal properties of nine quaternary dialkyldiaralkylammonium chlorides

Abstract Nine R 2 R 2 ′ N + Cl − (R=benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-phenylethyl or 3-phenylpropyl; R′=ethyl or methyl) quaternary dialkyldiaralkylammonium chlorides were synthesized by treating dimethylformamide or diethylformamide with non-substituted or substituted arylalkyl (aralkyl) halide in the presence of sodium carbonate. The 1H NMR, 13C NMR spectroscopy, mass spectroscopy and elemental analysis were used to characterize the synthesized products. The crystal structures of six compounds were determined by X-ray single crystal diffraction. Four of the compounds crystallized in monoclinic space groups C2/c and P21/c (or P21/n), one in triclinic space group P−1…

Dimeric Resorcin[4jarene Capsules in the Solid State

Supramolecular chemistry research is focused on the study of weak non-covalent intermolecular — that is, supramolecular — interactions as the driving force in self-assembly and molecular recognition. Dimeric resorcin[4]arenes capsules have been a focus of our research for the last 15 years. This review describes the solid state complexation studies of unsubstituted phenolic resorcin[4]arenes and pyrogall[4]arenes towards the formation of dimeric capsules and assemblies using ionic and neutral species as guest molecules and templates. The multitude of different crystal structures obtained during these studies demonstrates the versatile nature of resorcin[4]arenes and pyrogall[4]arenes (2-hyd…

Binding Properties of HABA-Type Azo Derivatives to Avidin and Avidin-Related Protein 4

Summary The chicken genome encodes several biotin-binding proteins, including avidin and avidin-related protein 4 (AVR4). In addition to D -biotin, avidin binds an azo dye compound, 4-hydroxyazobenzene-2-carboxylic acid (HABA), but the HABA-binding properties of AVR4 are not yet known. Differential scanning calorimetry, UV/visible spectroscopy, and molecular modeling were used to analyze the binding of 15 azo molecules to avidin and AVR4. Significant differences are seen in azo compound preferences for the two proteins, emphasizing the importance of the loop between strands β3 and β4 for azo ligand recognition; information on these loops is provided by the high-resolution (1.5 A) X-ray stru…

Halogen bonding drives the self-assembly of piperazine cyclophanes into tubular structures.

Halogen bonding with 1,4-diiodotetrafluorobenzene leads to the self-assembly of piperazine cyclophanes into well-defined tubular structures with solvent inclusion.

Macrocyclic Ethers and Their Inclusion Complexes

Mass spectrometric studies on pyridine-piperazine-containing ligands and their complexes with transition metals formed in solution.

Electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) methods were used to study open-chain piperazine-containing ligands (L) and their complexes formed with transition-metal salts. ESI and MALDI measurements were performed with a Fourier transform ion cyclotron resonance (FT-ICR) and a time-of-flight (TOF) mass spectrometer, respectively. Only singly charged complexes, between one ligand and one or several metal ions, were formed in the ESI measurements. Because the net charge was always one, one or several counterions were attached to the complex. Under ESI conditions, the complexes formed between the ligands and metal (Co, Ni, Cu, and Cd) salts were [L + M…

Chiral self-sorting behaviour of [2.2]paracyclophane-based bis(pyridine) ligands

Two constitutionally isomeric chiral bis(pyridine) ligands based on planar chiral 4,15-difunctionalized [2.2]paracyclophanes were synthesized, the respective enantiomers were separated via HPLC on a chiral stationary phase, and their self-assembly behaviour upon coordination to palladium(ii) ions was studied with regard to chiral self-sorting effects. As proven by NMR spectroscopy, mass spectrometry, CD spectroscopy, UV-Vis spectroscopy and X-ray crystallography both ligands form the expected dinuclear complexes upon coordination to cis-protected di- or tetravalent palladium(ii) ions, respectively, however, with distinct differences concerning their chiral self-sorting ability. peerReviewed

Two-component self-assembly with solvent leading to "wet" and microcrystalline organogel fibers

Abstract Hypothesis The microcrystalline fibers of N -(2-aminoethyl)-3α-hydroxy-5β-cholan-24-amide 1 provided a useful model system for studying the complex relationship between morphology, experimental parameters, solvent, and the phenomenon of organogelation. The presence of solvents in the solid forms of 1 along with crystallization behavior suggested solvate formation and polymorphic behavior. Experiments Forty solid state- and xerogel samples of 1 formed in organic solvents and in three categories of experimental conditions were analyzed with single crystal X-ray diffraction (XRD), powder X-ray diffraction (PXRD), Raman microscopy, and attenuated total reflection Fourier-transform infr…

Rotenoids, Flavonoids, and Chalcones from the Root Bark of Millettia usaramensis.

Five new compounds, 4-O-geranylisoliquiritigenin (1), 12-dihydrousararotenoid B (2), 12-dihydrousararotenoid C (3), 4'-O-geranyl-7-hydroxyflavanone (4), and 4'-O-geranyl-7-hydroxydihydroflavanol (5), along with 12 known natural products (6-17) were isolated from the CH2Cl2/MeOH (1:1) extract of the root bark of Millettia usaramensis ssp. usaramensis by chromatographic separation. The purified metabolites were identified by NMR spectroscopic and mass spectrometric analyses, whereas their absolute configurations were established on the basis of chiroptical data and in some cases also by X-ray crystallography. The crude extract was moderately active (IC50 = 11.63 μg/mL) against the ER-negative…

The pentafluorophenyl group as π-acceptor for anions: a case study† †This manuscript is dedicated to Prof. Jean-Marie Lehn on the occasion of his 75th birthday. ‡ ‡Electronic supplementary information (ESI) available. CCDC 967089, 967097, 1005267–1005289. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc02762k Click here for additional data file. Click here for additional data file.

A unique structural study investigates the variability of anion–π bonding in the solid state structures of pentafluorophenyl arenes. The hapticity concept is used as tool to describe the structural differences of various anion–π complexes.

Anion Recognition by a Bioactive Diureidodecalin Anionophore: Solid-State, Solution, and Computational Studies

Recent work has identified a bis-(p-nitrophenyl)ureidodecalin anion carrier as a promising candidate for biomedical applications, showing good activity for chloride transport in cells yet almost no cytotoxicity. To underpin further development of this and related compounds, a detailed structural and binding investigation is reported. Crystal structures of the transporter as five solvates confirm the diaxial positioning of urea groups while revealing a degree of conformational flexibility. Structures of complexes with Cl−, Br−, NO3 −, SO4 2− and AcO−, supported by computational studies, show how the binding site can adapt to accommodate these anions. 1H NMR binding studies revealed exception…

Flavonoids from Erythrina schliebenii

Prenylated and O-methylflavonoids including one new pterocarpan (1), three new isoflavones (2–4), and nineteen known natural products (5–23) were isolated and identified from the root, stem bark, and leaf extracts of Erythrina schliebenii. The crude extracts and their constituents were evaluated for antitubercular activity against Mycobacterium tuberculosis (H37Rv strain), showing MICs of 32–64 μg mL–1 and 36.9–101.8 μM, respectively. Evaluation of their toxicity against the aggressive human breast cancer cell line MDA-MB-231 indicated EC50 values of 13.0–290.6 μM (pure compounds) and 38.3 to >100 μg mL–1 (crude extracts).

Metal Doping of Au25(SR)18- Clusters : Insights and Hindsights

The structure, properties, and applications of atomically precise gold nanoclusters are the object of active research worldwide. Over the last few years, research has been also focusing on selective doping of metal nanoclusters through introduction of foreign-metal atoms. Doping has been studied for several clusters, especially the atomically precise Au25(SR)18. Doping has been carried out with noble metals, such as platinum, and less noble metals, such as cadmium and mercury, also because of the ease by which monodoping can be achieved with these metals. Previous studies, which relied extensively on the use of mass spectrometry and single crystal X-ray crystallography, led to assign the sp…

Dual-stimuli pseudorotaxane switches under kinetic control

A series of dumbbell-shaped sec-ammonium salts with bulky (pseudo)stoppers (‘speed bumps’) were tested for their ability to form pseudorotaxanes with a redox-switchable, tetrathiafulvalene (TTF)-decorated [24]crown-8 ether. Depending on the size of the pseudostoppers, fast (less than ten minutes), slow (hours to days) and very slow (no pseudorotaxanes observed) threading has been observed. NMR spectroscopy as well as tandem mass spectrometry indicate the formation of non-threaded face-to-face complexes prior to pseudorotaxanes formation. Both isomers can be distinguished by their substantially different stability in collision-induced dissociation (CID) experiments. Two external stimuli affe…

Electron-deficient trifluoromethyl-substituted sub-components affect the properties of M4L4 tetrahedral cages

Two supramolecular tetrahedral cages based on a new electron-deficient trifluoromethyl-substituted pyridylimine ligand are synthesised by sub-component self-assembly. Their structures are characterised by NMR und UV-Vis spectroscopy, high-resolution mass spectrometry and single crystal X-ray diffraction. The iron(II) complex shows host–guest chemistry, complex-to-complex transformations and novel electronic properties.

Coordinatively Unsaturated Lanthanide(III) Helicates: Luminescence Sensors for Adenosine Monophosphate in Aqueous Media

Coordinatively unsaturated double-stranded helicates [(H2 L)2 Eu2 (NO3 )2 (H2 O)4 ](NO3 )4 , [(H2 L)2 Tb2 (H2 O)6 ](NO3 )6 , and [(H2 L)2 Tb2 (H2 O)6 ]Cl6 (H2 L=butanedioicacid-1,4-bis[2-(2-pyridinylmethylene)hydrazide]) are easily obtained by self-assembly from the ligand and the corresponding lanthanide(III) salts. The complexes are characterized by X-ray crystallography showing the helical arrangement of the ligands. Co-ligands at the metal ions can be easily substituted by appropriate anions. A specific luminescence response of AMP in presence of ADP, ATP, and other anions is observed. Specificity is assigned to the perfect size match of AMP to bridge the two metal centers and to replac…

Recognition-Directed Supramolecular Assemblies of Metal Complexes of Terpyridine Derived Ligands with Self-Complementary Hydrogen Bonding Sites

The synthesis and X-ray structures of three metal complexes with terpyridine-derived ligands that contain amino-pyrimidine and amino-pyrazine moieties are presented. They have been designed in view of directing their self-assembly into specific supramolecular arrays through molecular recognition interactions. The solid-state structures indeed reveal extensive hydrogen-bonded networks. The Co complex 4a with PF6- counterions builds a two-dimensional infinite interwoven grid through strong double hydrogen bonds (d(N-H-N) =2.918-3.018 A) between the amino groups and the N atoms of the rings, with all H-bonding sites saturated. Changing the anions to BF4- in 4b leads to a similar infinite but p…

Reliable fluorescence technique to detect the antibiotic colistin, a possible environmental threat due to its overuse.

AbstractColistin, considered a drug of last resort as it is effective towards multidrug-resistant Gram-negative bacterial infections. Oral administration of colistin in the poultry industry is a common practice, not only to prevent and reduce bacterial infections, but also as a rapid-growth promoter. Long-term exposure to any antibiotic will eventually lead to the development of bacterial resistance towards all antibiotics through various mechanisms in the physiological system and environment. Chicken is the most consumed source of animal protein for humans throughout the world. In addition, the manure of poultry, containing traces of the used antibiotics, is being used in farming. Exposure…

A coumarin based gold(I)-alkynyl complex: a new class of supramolecular hydrogelators

A phosphine-gold(I)-alkynyl-coumarin complex, [Au{7-(prop-2-ine-1-yloxy)-1-benzopyran-2-one}- (DAPTA)] (1), was synthesized and the formation of long luminescent fibers in solution was characterized via fluorescence microscopy and dynamic light scattering. The fibers presented strong blue and green luminescence, suggesting that the gold(I) in the complex increased intersystem crossing due to the heavy atom effect, resulting in a significant increase in triplet emission. The X-ray structure of the fibers indicates that both aurophilic, π–π interactions and hydrogen bonding contribute to their formation in aqueous solvents. peerReviewed

Mechanochemical Syntheses of N-Containing Heterocycles with TosMIC

A mechanochemical van Leusen pyrrole synthesis with a base leads to 3,4-disubstitued pyrroles in moderate to excellent yields. The developed protocol is compatible with a range of electron-withdrawing groups and can also be applied to the synthesis of oxazoles. Attempts to mechanochemically convert the resulting pyrroles into porphyrins proved to be difficult.

Schiff-Base Podates – X-ray, NMR and Ab Initio Molecular-Orbital Studies of the Cadmium(II) Complexes of Linear and Three-Armed Podands in Solution and Solid State

Cadmium(II) complexes of two Schiff bases, 1,3-di(pyridine-2-carboxaldimino)propane (C15H16N4, L1)[1] and tris[4-(2′-pyridyl)-3-aza-3-butenyl]amine (C24H27N7, L2)[2] are described. An efficient route utilising molecular sieves for the synthesis of Schiff bases is presented. The ligands L1 and L2 can be described as linear and three-armed podands, respectively, L1 being conformationally flexible and L2 preorganised. Cadmium perchlorate in methanol with L1 yields a crystalline complex [Cd(L1)2](ClO4)2 (1), the structure of which was determined by X-ray structure analysis. The complex 1 has an unusual nonsymmetrical 8-coordinated helical structure and crystallizes in an acentric space group (C…

A 2,3-dialkoxynaphthalene-based naphthocage

A 2,3-dialkoxynaphthalene-based naphthocage has been synthesized. This naphthocage prefers to bind small organic cations with its low-symmetry conformation, which is in contrast to 2,6-dialkoxynaphthalene-based naphthocages. Self-sorting of these two naphthocages with two structurally similar guests tetramethylammonium and tetraethylammonium was achieved as well. peerReviewed

Halogen Bonds in 2,5-Dihalopyridine-Copper(I) Halide Coordination Polymers

Two series of 2,5-dihalopyridine-Cu(I)A (A = I, Br) complexes based on 2-X-5-iodopyridine and 2-X-5-bromopyridine (X = F, Cl, Br and I) are characterized by using single-crystal X-ray diffraction analysis to examine the nature of C2&minus

Revisiting the bromination of 3β-hydroxycholest-5-ene with CBr4/PPh3 and the subsequent azidolysis of the resulting bromide, disparity in stereochemical behavior

Cholesterol reacts under Appel conditions (CBr4/PPh3) to give 3,5-cholestadiene (elimination) and 3β-bromocholest-5-ene (substitution with retention of configuration). Thus, the bromination of cholesterol deviates from the stereochemistry of the standard Appel mechanism due to participation of the Δ5 π-electrons. In contrast, the subsequent azidolysis (NaN3/DMF) of 3β-bromocholest-5-ene proceeds predominantly by Walden inversion (SN2) affording 3α-azidocholest-5-ene. The structures of all relevant products were revealed by X-ray single crystal structure analyses, and the NMR data are in agreement to the reported ones. In light of these findings, we herein correct the previous stereochemical…

Selective guest inclusion of linear C6 hydrocarbons in a Zn(ii) 1D coordination polymer

Trapping of volatile unbranched C6 hydrocarbons (hexane, 1-hexene, and 1-hexyne) in a 1D coordination polymer is reported. The guest inclusion was studied quantitatively by 1H-NMR analysis and thermogravimetric measurements, while synchrotron single-crystal diffraction data allowed advancing the view of their confinement into linear CP channels. Adsorption experiments performed through solid/vapour processes on microcrystals of CP 1 showed a certain degree of selectivity for 1-hexyne, which could be rationalized by its larger dipole moment.

Electron-deficient trifluoromethyl-substituted sub-components affect the properties of M4L4 tetrahedral cages

Two supramolecular tetrahedral cages based on a new electron-deficient trifluoromethyl-substituted pyridylimine ligand are synthesised by sub-component self-assembly. Their structures are characterised by NMR und UV-Vis spectroscopy, high-resolution mass spectrometry and single crystal X-ray diffraction. The iron(II) complex shows host–guest chemistry, complex-to-complex transformations and novel electronic properties. peerReviewed

Influencing the Self‐Sorting Behavior of [2.2]Paracyclophane‐Based Ligands by Introducing Isostructural Binding Motifs

Abstract Two isostructural ligands with either nitrile (Lnit) or isonitrile (Liso) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself (Lnit) or its precursors (Liso) were resolved by HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum‐chemical simulated and experimental electronic circular dichroism (ECD) spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf)2] differ in their composition: whereas Lnit forms dinuclear complexes, Liso…

Inclusion complexes of Cethyl-2-methylresorcinarene and pyridine N-oxides: breaking the C–I⋯−O–N+ halogen bond by host–guest complexation

C ethyl-2-Methylresorcinarene forms host–guest complexes with aromatic N-oxides through multiple intra- and intermolecular hydrogen bonds and C–H⋯π interactions. The host shows conformational flexibility to accommodate 3-methylpyridine N-oxide, while retaining a crown conformation for 2-methyl- and 4-methoxypyridine N-oxides highlighting the substituent effect of the guest. N-Methylmorpholine N-oxide, a 6-membered ring aliphatic N-oxide with a methyl at the N-oxide nitrogen, is bound by the equatorial −N–CH3 group located deep in the cavity. 2-Iodopyridine N-oxide is the only guest that manifests intermolecular N–O⋯I–C halogen bond interactions, which are broken down by the host resulting i…

A highly selective, Hg2+ triggered hydrogelation: modulation of morphology by chemical stimuli

We report the first Hg2+ selective hydrogelation by 4´-[4-(4- aminophenyl)phenyl]-2,2´:6´,2´´-terpyridine. The gel showed remarkable response towards specific chemical agents such as benzo-18-crown-6 ether and K+ which enabled extensive 10 modulation of the gel morphology. peerReviewed

Selective encapsulation of a chloride anion in a 1H-pyrazole Cu2+ metallocage

A self-assembled metallobox from copper(ii) and two macrocycles containing 1H-pyrazole ligands has been prepared. The internal cavity of the box is able to selectively encapsulate a single chloride anion over any other halide anion.

Spin Crossover in a Supramolecular Fe4II [2×2] Grid Triggered by Temperature, Pressure, and Light

A multiplex electronic switch on the molecular level has been realized by using a tetranuclear FeII complex of the [2×2] grid type. The four metal ions can be switched stepwise between their high-spin and low-spin states by temperature, pressure, and light, thus representing a triple level, triple switch system as illustrated in the picture.

Rapid self-healing and anion selectivity in metallosupramolecular gels assisted by fluorine-fluorine interactions.

Simple ML2 [M = Fe(II), Co(II), Ni(II)] complexes obtained from a perfluoroalkylamide derivative of 4-aminophenyl-2,2′,6,2′-terpyridine spontaneously, yet anion selectively, self-assemble into gels, which manifest an unprecedented rapid gel strength recovery, viz. self-healing, and thermal rearrangement in aqueous dimethyl sulfoxide. The key factor for gelation and rheological properties emerges from the fluorine–fluorine interactions between the perfluorinated chains, as the corresponding hydrocarbon derivative did not form metallogels. The perfluoro-terpyridine ligand alone formed single crystals, while its Fe(II), Co(II) or Ni(II) complexes underwent rapid gelation leading to highly enta…

Size‐Selective Encapsulation of Hydrophobic Guests by Self‐Assembled M 4 L 6 Cobalt and Nickel Cages

Subtle differences in metal-ligand bond lengths between a series of [M(4)L(6)](4-) tetrahedral cages, where M = Fe(II), Co(II), or Ni(II), were observed to result in substantial differences in affinity for hydrophobic guests in water. Changing the metal ion from iron(II) to cobalt(II) or nickel(II) increases the size of the interior cavity of the cage and allows encapsulation of larger guest molecules. NMR spectroscopy was used to study the recognition properties of the iron(II) and cobalt(II) cages towards small hydrophobic guests in water, and single-crystal X-ray diffraction was used to study the solid-state complexes of the iron(II) and nickel(II) cages.

Encapsulation of xenon by bridged resorcinarene cages with high 129Xe NMR chemical shift and efficient exchange dynamics

Functionalized cages encapsulating xenon atoms enable highly sensitive, background-free molecular imaging through a technique known as HyperCEST 129Xe MRI. Here, we introduce a class of potential biosensor cage structures based on two resorcinarene macrocycles bridged either by aliphatic carbon chains or piperazines. First-principles-based modeling predicts a high chemical shift (about 345 ppm) outside the typical experimental observation window for 129Xe encapsulated by the aliphatically bridged cage and two 129Xe resonances for the piperazine-bridged cages corresponding to single and double loading. Based on the computational predictions as well as 129Xe chemical exchange saturation trans…

Host-Guest Interactions of Sodiumsulfonatomethyleneresorcinarene and Quaternary Ammonium Halides : An Experimental-Computational Analysis of the Guest Inclusion Properties

The molecular recognition of nine quaternary alkyl- and aryl-ammonium halides (Bn) by two different receptors, Calkyl-tetrasodiumsulfonatomethyleneresorcinarene (An), were studied in solution using 1H NMR spectroscopy. Substitution of methylenesulfonate groups at 2-positions of resorcinol units resulted in an increase of cavity depth by ∼2.80 Å and a narrow cavity aperture compared to Calkyl-2-H-resorcinarenes. The effect of alkyl chain lengths on the endo-complexation, that is the ability to incorporate other than N-methyl chains inside the cavities, were investigated using ammonium cations of the type ⁺NH2(R1)(R2), (R1 = Me, Et, Bu, R2 = Bu, Ph, Bz ). The C−H⋯ interactions between guests …

Expanding the Size of Catecholesters - Modified Ligands for the Hierarchical Assembly of Dinuclear Titanium(IV) Helicates

Five 2,3-dihydroxybenzoic acid derivatives 1 – 5 were used as starting materials to obtain the corresponding methyl and ethyl esters. Those were applied as ligands in the hierarchical self-assembly of lithium-bridged dinuclear titanium(IV) complexes 1a–4a, 1b–3b, and 5b. The equilibria between the mononuclear triscatecholate complexes (monomer) and the dinuclear helicates (dimer) were observed by 1H NMR spectroscopy in [D6]DMSO and [D4]MeOH at room temperature.

Dimensional encapsulation of I− I 2 I− in an organic salt crystal matrix

Bis(trimethylammonium)hexane diiodide encapsulates iodine from solution and through a gas/solid reaction yielding in a predictable and controllable manner the selective formation of the rare polyiodide species I(-)...I-I...I(-), which matches in length to the chosen dication.

Enantioselective Total Syntheses of (+)-Hippolachnin A, (+)-Gracilioether A, (-)-Gracilioether E and (-)-Gracilioether F

The Plakortin polyketides represent a structurally and biologically fascinating class of marine natural products. Herein, we report a unified strategy that enables the divergent syntheses of various Plakortin polyketides with high step-economy and overall efficiency. As proof-of-concept cases, the enantioselective total syntheses of (+)-hippolachnin A, (+)-gracilioether A, (−)-gracilioether E, and (−)-gracilioether F have been accomplished based on a series of bio-inspired, rationally designed, or serendipitously discovered transformations, which include (1) an organocatalytic asymmetric 1,4-conjugate addition to assemble the common chiral γ-butenolide intermediate enroute to all of the afo…

The Synergetic Interplay of Weak Interactions in the Ion-Pair Recognition of Quaternary and Diquaternary Ammonium Salts by Halogenated Resorcinarenes

The influence of halogens on the noncovalent interactions of different upper-rim-substituted hexylresorcinarenes with quaternary and diquaternary ammonium iodide salts was investigated in the gas phase by electrospray ionization Fourier-transform ion-cyclotron-resonance (ESI-FTICR) mass spectrometry and in solution by 1H NMR titration studies. The electronic nature of the substituents on the upper rim of the resorcinarene was directly reflected in the order of binding strengths of the hosts towards quaternary and diquaternary ammonium cations in the gas phase. In solution, the opposite trend was observed, with generally higher binding constants for the diquaternary over the quaternary salts…

A Trinuclear Aqua Cyano‐Bridged Ruthenium Complex [{(η 5 ‐C 5 H 5 )(PPh 3 ) 2 Ru(μ‐CN)} 2 RuCl 2 (PPh 3 )(H 2 O)]PF 6 : Synthesis, Characterization and Crystal Structure

The organometallic trinuclear aqua cyano-bridged complex [{(η5-C5H5)(PPh3)2Ru(μ-CN)}2RuCl2(PPh3)(H2O)]PF6 (1), in which the fragment [RuCl2(PPh3)(H2O)] acts as a bridge and an acceptor group between the two terminal cyclopentadienyl ruthenium cyano moieties, was isolated in moderate yield from the reaction of [(η5-C5H5)(PPh3)2RuCN] with [RuCl2(PPh3)3] in THF. To the best of our knowledge, compound 1 is one of the few examples of a trinuclear array of ruthenium fragments bridged by the nitrogen atom of the–C≡N– group (Ru–C≡N–Ru′–N≡C–Ru) with a Ru-coordinated water molecule. The new aqua complex was structurally characterized by FTIR, 1H, 13C, and 31P NMR spectroscopy, mass spectrometry, elem…

Template-controlled synthesis of chiral cyclohexylhemicucurbit[8]uril

Enantiomerically pure cyclohexylhemicucurbit[8]uril (cycHC[8]), possessing a barrel-shaped cavity, has been prepared in high yield on a gram scale from either (R,R,N,N')-cyclohex-1,2-diylurea and formaldehyde or cycHC[6]. In either case, a dynamic covalent library is first generated from which the desired cycHC can be amplified using a suitable anion template.

Synthesis of 2-anilinobenzimidates, anthranilamides, and 2,3-dihydroquinazolin-4(1H)-ones from N-heterocyclic carbenes of indazole

N-Heterocyclic carbenes of indazole (indazol-3-ylidenes), which are substituted at N1 with aromatics were generated in situ from the corresponding indazolium salts. At 60 °C the indazol-3-ylidenes underwent a ring-opening under N–N bond cleavage to intermediary N-(6-methylenecyclohexa-2,4-dien-1-ylidene)anilines. Trapping of these intermediates by alcohols proved to be a convenient method for the preparation of 2-anilinobenzimidates, which have scarcely been described in the literature. The reaction temperature avoids carbene dimerization, which occurs at −80 °C or rearrangement of the ring-opened intermediate to acridines, which affords 100 °C. Water converted the ring-opened products into…

An Extraction-Based Assay for Neutral Anionophores: The Measurement of High Binding Constants to Steroidal Receptors in a Nonpolar Solvent

The extraction-based proto- col for measuring binding constants, developed by Cram and co-workers, has been extended for use with anionic substrates. The method is especially useful for high-affinity receptors, allow- ing very high binding constants to be measured in nonpolar solvents. Distri- bution constants Kd between chloroform and water have been obtained for tet- raethylammonium chloride and bro- mide, thus calibrating the method for these two substrates. Application to steroidal podands 5 ± 9 has confirmed the ability of electron-withdrawing groups to enhance hydrogen-bond do- nor capabilities. Binding constants of 3 10 71 have been measured for the most powerful receptor 7. An X-ray…

Thermodynamic and electrochemical study of tailor-made crown ethers for redox-switchable (pseudo)rotaxanes

Crown ethers are common building blocks in supramolecular chemistry and are frequently applied as cation sensors or as subunits in synthetic molecular machines. Developing switchable and specifically designed crown ethers enables the implementation of function into molecular assemblies. Seven tailor-made redox-active crown ethers incorporating tetrathiafulvalene (TTF) or naphthalene diimide (NDI) as redox-switchable building blocks are described with regard to their potential to form redox-switchable rotaxanes. A combination of isothermal titration calorimetry and voltammetric techniques reveals correlations between the binding energies and redox-switching properties of the corresponding ps…

Synthesis of trans-disubstituted-2,3-dihydrobenzofurans by a formal [4 + 1] annulation between para-quinone methides and sulfonium salts

An efficient protocol for the synthesis of trans-disubstituted-2,3-dihydrobenzofurans through [4 + 1] annulation of para-quinone methides with sulfonium salts has been developed. Under very mild conditions this unprecedented reaction occurs in good to excellent yields (up to 99%), offering a straightforward access to a variety of 2,3-dihydrobenzofurans.

Supramolecular assemblies and photophysical properties of ionic homo- and heteronuclear metallophilic complexes

Abstract The synthesis of two dinuclear ionic complexes with chemical formula [Au(PR 3 ) 2 ][Au(C ≡ CC 5 H 4 N-4) 2 ] that contain the water soluble phosphines, PR 3 , PTA (1, 3,5-triaza-7-phosphaadamantane, 1 ) and DAPTA (3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane, 2 ) is herein described. The differences on their intermolecular reorganization have been analyzed and compared with the previously reported for the neutral complexes [Au(PR 3 )(C ≡ CC 5 H 4 N-4)]. It has been evidenced that the reorganization of the ligands giving rise to the dinuclear ionic complexes produces a complete change in the properties giving rise to Au⋯Au intermolecular assemblies. These aurophilic conta…

Halogen Bonds in Square Planar 2,5-Dihalopyridine-Copper(II) Bromide Complexes

Macrocyclic complexes based on [N⋯I⋯N]+ halogen bonds

New 1–2 nm macrocyclic iodine(I) complexes prepared VIA a simple ligand exchange reaction manifest rigid 0.5–1 nm cavities that bind the hexafluorophosphate anion in the gas phase. The size of the cavities and the electrostatic interactions with the iodine(I) cations influence the anion binding properties of these macrocyclic complexes. peerReviewed

E-Ring extended estrone derivatives: introduction of 2-phenylcyclopentenone to the estrone D-ring via an intermolecular Pauson–Khand reaction

Abstract An expedient synthetic route to E-ring extended estrone derivatives is reported. Estrone-derived cyclopentenones were accessed by an intermolecular Pauson–Khand (PK) cycloaddition. It was found that electron donating and withdrawing substituents in the arylalkyne increased and decreased the yields of PK products, respectively. The stereochemistry of the products was elucidated by X-ray and NMR studies.

Synthesis, structure and photophysical properties of a highly luminescent terpyridine-diphenylacetylene hybrid fluorophore and its metal complexes

A new fluorescent terpyridyl-diphenylacetylene hybrid fluorophore 4'-[4-{(4-methoxyphenyl)ethynyl}phenyl]-2,2':6',2''-terpyridine, L, was synthesized via Sonogashira cross-coupling of 4'-(4-bromophenyl)-2,2':6',2''-terpyridine and 4-ethynylanisole in the presence of Pd(PPh3)4/CuI as a catalyst. The solid state structure of L shows a trans arrangement of pyridine nitrogen atoms along the interannular bond in the terpyridine domain. Five transition metal complexes of L, {[FeL2](CF3SO3)2 (1), [ZnL2](ClO4)2 (2), [CdL2](ClO4)2 (3), [RuL2](PF6)2 (4), and PtMe3IL (5)}, have also been synthesized and characterized by spectroscopic methods and single crystal X-ray analysis. The X-ray crystal structu…

Luminescent Pt-II and Pt-IV Platinacycles with Anticancer Activity Against Multiplatinum-Resistant Metastatic CRC and CRPC Cell Models

Platinum-based chemotherapy persists to be the only effective therapeutic option against a wide variety of tumours. Nevertheless, the acquisition of platinum resistance is utterly common, ultimately cornering conventional platinum drugs to only palliative in many patients. Thus, encountering alternatives that are both effective and non-cross-resistant is urgent. In this work, we report the synthesis, reduction studies, and luminescent properties of a series of cyclometallated (C,N,N')PtIV compounds derived from amine- imine ligands, and their remarkable efficacy at the high nanomolar range and complete lack of cross57 resistance, as an intrinsic property of the platinacycle, against multipl…

Organocatalytic Asymmetric Synthesis of Trifluoromethylated Tetrahydrocarbazoles by a Vinylogous Michael/Aldol Formal [4+2] Annulation

Strong N−X⋅⋅⋅O−N Halogen Bonds: A Comprehensive Study on N‐Halosaccharin Pyridine N ‐Oxide Complexes

A study of the strong N-X⋅⋅⋅- O-N+ (X=I, Br) halogen bonding interactions reports 2×27 donor×acceptor complexes of N-halosaccharins and pyridine N-oxides (PyNO). DFT calculations were used to investigate the X⋅⋅⋅O halogen bond (XB) interaction energies in 54 complexes. A simplified computationally fast electrostatic model was developed for predicting the X⋅⋅⋅O XBs. The XB interaction energies vary from -47.5 to -120.3 kJ mol-1 ; the strongest N-I⋅⋅⋅- O-N+ XBs approaching those of 3-center-4-electron [N-I-N]+ halogen-bonded systems (ca. 160 kJ mol-1 ). 1 H NMR association constants (KXB ) determined in CDCl3 and [D6 ]acetone vary from 2.0×100 to >108  m-1 and correlate well with the calculat…

N-Alkyl ammonium resorcinarene salts: multivalent halogen-bonded deep-cavity cavitands

A highly selective, Hg2+ triggered hydrogelation: modulation of morphology by chemical stimuli

We report the first Hg(2+) selective hydrogelation by 4'-[4-(4-aminophenyl)phenyl]-2,2':6',2''-terpyridine. The gel showed remarkable response towards specific chemical agents such as benzo-18-crown-6 ether and K(+) which enabled extensive modulation of the gel morphology.

Asymmetric Organocatalytic Wittig [2,3]-Rearrangement of Oxindoles

A highly enantioselective organocatalytic [2,3]-rearrangement of oxindole derivatives is presented. The reaction was catalyzed by squaramide, and this provides access to 3-hydroxy 3-substituted oxindoles in high enantiomeric purities.

2-Methylresorcinarene: a very high packing coefficient in a mono-anion based dimeric capsule and the X-ray crystal structure of the tetra-anion

Mono- and tetra-deprotonated 2-methylresorcinarene anions (1 and 2) as their trans-1,4-diammoniumcyclohexane (TDAC)2+ inclusion complexes are reported. The mono-anion forms a fully closed dimeric capsule [1·H2O·MeOH]22− with a cavity volume of 165 Å3 and (TDAC)2+ as the guest with an extremely high packing coefficient, PC = 84.2%, while the tetra-anion forms a close-packed structure with two structurally isomeric tetra-anions 2a and 2b with a 50 : 50 ratio in the crystal lattice. peerReviewed

Mono-, di- and tri-nuclear Ni(II) complexes of N-, O-donor ligands: structural diversity and reactivity

A series of mono-, di- and tri-nuclear Ni(II) complexes of N, O-donating molecules possessing ---H2C---NH--- and ---HC=N--- moieties have been synthesized and characterized and the structures have been determined by single crystal X-ray diffraction. All these exhibited interesting molecular packing in their crystal lattices. Di-nuclear complexes were found to be cleaved in pyridine to result in mononuclear ones with additional coordinations being provided by pyridine. Di-nuclear complexes were found to form urea adducts as demonstrated based on absorption and vibrational studies.

C-Methyl resorcin[4]arene packing motifs with alkyl ammonium salts: From molecular capsules to channels and tubes

A variety of packing motifs of C-methyl resorcinarene were obtained when complexed with small alkyl ammonium salts of different size and shape. Using bromide and chloride salts of the small quaternary alkyl ammonium cations, tetramethyl ammonium and dimethyldiethyl ammonium, leads to a grid-like packing of solvent mediated dimeric capsules while the use of salts of larger diquaternary cations bearing a 1,4-diazabicyclo[2.2.2]octane (DABCO) scaffold produces solvent/anion mediated chains and channels or tubular structures. The connecting interactions between resorcinarenes in each structure are hydrogen bonding and/or π⋯π interactions.

Deprotonation of resorcinarenes by mono- and diamine bases: complexation and intermolecular interactions in the solid state

The deprotonation of resorcinarenes by mono- and dibasic amines, viz. triethylamine (TEA) and its dibasic analogue, N,N′-dimethylpiperazine (DMPip), was studied and the resulting supramolecular complexes were analysed in the solid state, in solution and in the gas phase. In the solid state, 1:1 (2TEAH+·(ethyl-resorcinarene)2−·MeOH), 3:2 [DMPip·2DMPipH+·2(ethyl-resorcinarene−)] and 3:2 [2DMPip·DMPipH22+@(2methyl-ethyl-resorcinarene−)2·2MeOH] solid state complexes and interesting resorcinarene−⋯resorcinarene− supramolecular networks formed via enhanced hydrogen bonds involving the hydroxyl groups and the deprotonated hydroxyl groups of the resorcinarenes were observed. The host–guest complexe…

Cyclic Sulfoximine and Sulfonimidamide Derivatives by Copper‐Catalyzed Cross‐Coupling Reactions with Elemental Sulfur

Copper-catalyzed cross-coupling reactions of α-bromoaryl NH-sulfoximines with elemental sulfur lead to benzo[d][1,3,2]dithiazole-1-oxides, which represent a new class of three-dimensional heterocycles. The reactions proceed under mild conditions showing good functional group and heterocycle tolerance. By imination/oxidation, the initial cross-coupling products can be converted to unprecedented cyclic sulfonimidamides derivatives. Furthermore, a seven-membered heterocycle was obtained by a ruthenium-catalyzed ring-expansion with ethyl propiolate. peerReviewed

Directional Shuttling of a Stimuli-Responsive Cone-Like Macrocycle on a Single-State Symmetric Dumbbell Axle

Rotaxane-based molecular shuttles are often operated using low-symmetry axles and changing the states of the binding stations. A molecular shuttle capable of directional shuttling of an acid-responsive cone-like macrocycle on a single-state symmetric dumbbell axle is now presented. The axle contains three binding stations: one symmetric di(quaternary ammonium) station and two nonsymmetric phenyl triazole stations arranged in opposite orientations. Upon addition of an acid, the protonated macrocycle shuttles from the di(quaternary ammonium) station to the phenyl triazole binding station closer to its butyl groups. This directional shuttling presumably originates from charge repulsion and an …

Bipyridine based metallogels: an unprecedented difference in photochemical and chemical reduction in the in situ nanoparticle formation

Metal co-ordination induced supramolecular gelation of low molecular weight organic ligands is a rapidly expanding area of research due to the potential in creating hierarchically self-assembled multi-stimuli responsive materials. In this context, structurally simple O-methylpyridine derivatives of 4,4′-dihydroxy-2,2′-bipyridine ligands are reported. Upon complexation with Ag(I) ions in aqueous dimethyl sulfoxide (DMSO) solutions the ligands spontaneously form metallosupramolecular gels at concentrations as low as 0.6 w/v%. The metal ions induce the self-assembly of three dimensional (3D) fibrillar networks followed by the spontaneous in situ reduction of the Ag-centers to silver nanopartic…

Recent Advances in Halogen Bonded Assemblies with Resorcin[4]arenes

Resorcinarenes are cavity-containing compounds when in the crown conformation, from the calixarene family of concave compounds. These easy to synthesize macrocycles can be decorated at the upper rim through the eight hydroxyl groups and/or the 2-position of the aromatic ring. They are good synthons in supramolecular chemistry leading to appealing assemblies such as open-inclusion complexes, capsules and tubes through multiple weak interactions with various guests. Halogen bonding (XB) is a highly directional non-covalent interaction by an electron-deficient halogen atom as a donor that interacts with a Lewis base, the XB acceptor. This tutorial review provides an overview of recent advances…

Introduction of a luminescent sensor for tracking trace levels of hydrazine in insect pollinated cropland flowers

In recent years the excessive use of hydazine containing chemical pesticides and insecticides in farming practices is well pronounced, which directly or indirectly impart a great threat towards the total environment. Considering the above fact we are motivated to introduce a new, efficient and simple chemodosimeter (NCD) based on a carbazole-naphthalimide framework to recognize and estimate the mutagenic hydrazine within several affected cropland flowers. Probe NCD can detect hydrazine in a nanomolar range (65 nM or 2 ppb) in the presence of other metal ions, anions and amines, which gives it not only great potential but also makes it selective and sensitive. The sensing mechanism is confir…

Spontaneous Resolution of an Electron‐Deficient Tetrahedral Fe4L4cage

A highly electron-deficient C3-symmetric tris(bipyridyl) ligand was prepared in four steps and used for the coordination of Fe(OTf)2, thereby resulting in the homochiral assembly of a new family of robust tetrahedral M4L4 cages. This homochiral T-symmetric cage containing a relatively large cavity of 330 A(3) is capable of encapsulating an anionic guest, as was determined by mass spectrometry, (19)F NMR spectroscopy, and finally shown from its crystal structure. Moreover, crystallization of the cage from CH3CN led to crystals containing both (ΔΔΔΔ and ΛΛΛΛ) enantiomers, while crystallization from CH3 OH resulted in crystals containing only the right-handed (ΔΔΔΔ) cage. The difference in the…

N-Alkyl ammonium resorcinarene polyiodides

Four N-alkyl ammonium resorcinarene halides incorporating polyiodides were obtained and structurally analyzed by single crystal X-ray crystallography. The unexpected formation of triiodides and pentaiodide anions in these structures was assumed to be the result of the heterolytic dissociation of molecular iodine (I2) in the presence of electron donors in the N-alkyl ammonium resorcinarene halide system, from which I− further binds one or two I2 molecules resulting in I3− or I5− species, respectively.

Controlling the position of anions relative to a pentafluorophenyl groupw

The position of an anion above an electron-deficient arene can be controlled by the geometry of appended directing groups. Here a series of ammonium substituted pentafluorophenyl derivatives is investigated. The presented results are one step on the way to find the ideal structural features for an effective and superior receptor for anion–π studies.

From isolated 1H-pyrazole cryptand anion receptors to hybrid inorganic-organic 1D helical polymeric anion receptors

We report a novel 1-D helical coordination polymer formed by protonated polyamine 1H-pyrazole cryptands interconnected by Cu2+ metal ions that are able to encapsulate anionic species behaving as a multianion receptor. Switching from a monomeric receptor to a polymeric receptor is activated by metal ions and pH.

5-Carbonyl-1,3-oxazine-2,4-diones from N-Cyanosulfoximines and Meldrum’s Acid Derivatives

At elevated temperatures, N-cyanosulfoximines react with Meldrum’s acid derivatives to give sulfoximines with N-bound 5-carbonyl-1,3-oxazine-2,4-dione groups. A representative product was characterized by single-crystal X-ray structure analysis. The product formation involves an unexpected molecular reorientation requiring several sequential bond-forming and -cleaving processes. peerReviewed

“Two-Story” Calix[6]arene-Based Zinc and Copper Complexes: Structure, Properties, and O 2 Binding

International audience; A new “two-story” calix[6]arene-based ligand was synthesized, and its coordination chemistry was explored. It presents a tren cap connected to the calixarene small rim through three amido spacers. X-ray diffraction studies of its metal complexes revealed a six-coordinate ZnII complex with all of the carbonyl groups of the amido arms bound and a five-coordinate CuII complex with only one amido arm bound. These dicationic complexes were poorly responsive toward exogenous neutral donors, but the amido arms were readily displaced by small anions or deprotonated with a base to give the corresponding monocationic complexes. Cyclic voltammetry in various solvents showed a r…

Noncovalent assembly of functional groups on calix[4]arene molecular boxes

Calix[4]arenes diametrically substituted at the upper rim with two melamine units spontaneously form well-defined box-like assemblies in the presence of two equivalents of 5,5-diethylbarbituric acid. These assemblies, consisting of nine different components, are held together by 36 hydrogen bonds and are stable in apolar solvents at concentrations of up to 10-4M. This paper reports the first X-ray crystal structure, and the MALDI TOF mass spectra together with the complete 1H NMR spectroscopic characterization of these hydrogen-bonded assemblies. The crystal structure clearly shows that the assemblies are stereogenic, as a result of the antiparallel orientation of the two rosette motifs. Fu…

A new hydrogen bonding motif involved in self-recognition in the solid state by functionalised macrocycles

Self-recognition within the crystal lattices of three functionalised macrocycles results in the formation of arrays of remarkably similar hermaphroditic pairs of macrocycles. In the case of two of the macrocycles containing acylhydrazine substituents, a hitherto unknown recognition pattern is found in the interaction of the hydrazine moiety with crown-ether oxygen atoms.

Concerted halogen and hydrogen bonding in [RuI2(H2dcbpy)(CO)2]···I2···(CH3OH)···I2···[RuI2(H2dcbpy)(CO)2].

A new type of concerted halogen bond-hydrogen bond interaction was found in the solid state structure of [RuI(2)(H(2)dcbpy)(CO)(2)]···I(2)···(MeOH)···I(2)···[RuI(2)(H(2)dcbpy)(CO)(2)]. The iodine atoms of the two I(2) molecules interact simultaneously with each other and with the OH group of methanol of crystallization. The interaction was characterized by single crystal X-ray measurements and by computational charge density analysis based on DFT calculations.

Substituent Effect in 2-Benzoylmethylenequinoline Difluoroborates Exhibiting Through-Space Couplings. Multinuclear Magnetic Resonance, X-ray Diffraction, and Computational Study

The series of nine 2-benzoylmethylenequinoline difluoroborates have been synthesized and characterized by multinuclear magnetic resonance, X-ray diffraction (XRD), and computational methods. The through-space spin-spin couplings between (19)F and (1)H/(13)C nuclei have been observed in solution. The NMR chemical shifts have been correlated to the Hammett substituent constants. The crystal structures of six compounds have been solved by XRD. For two derivatives the X-ray wave function refinement was performed to evaluate the character of bonds in the NBF(2)O moiety by topological and integrated bond descriptors.

N-Alkyl Ammonium Resorcinarene Salts: A Versatile Family of Calixarene-Related Host Molecules

This chapter presents a review of the recent advances in the chemistry of N-alkylammonium resorcinarenes salt receptors. The Mannich condensation between amines (primary and secondary) and resorcinarenes result in resorcinarene tetrabenzoxazines and tetra-azoxazines. Only 2 isomers out of 16 potential isomers are formed. The resorcinarene tetrabenzoxazines possess deeper cavities than the parent resorcinarenes which are suitable for binding neutral and cationic guests. In the presence of mineral acids, the six-membered oxazine ring in the resorcinarene tetrabenzoxazines is opened, resulting in N-alkylammonium resorcinarene salts (NARSs). The NARSs possess four spatially-fixed anions within …

2-(2-Iodoethyl)isoindole-1,3-dione

The title compound, C10H8INO2, is an N-substituted phthalimide derivative in which the crystallographic inter­molecular contact pattern consists of I⋯I, C—H⋯I, C—H⋯O and aromatic π–π inter­actions.

Synthesis of N‐Fused Indolines via Copper (II)‐Catalyzed Dearomatizing Cyclization of Indoles

Advanced synthesis &amp; catalysis 363(12), 3121-3126 (2021). doi:10.1002/adsc.202100290

(Dimethylformamide)dioxobis(pentane-2,4-dionato)uranium(VI)

The title complex, [UO2(C5H7O2)2(C3H7NO)], was obtained as an unexpected product from our attempts to prepare UIV complexes with imine-type ligands. The title complex was also prepared directly from [UO2(OAc)2]·2H2O, pentane-2,4-dione and DMF. The UVI atom has a penta­gonal-bipyramidal geometry and is surrounded by seven O atoms. The bond distances and angles are similar to those found previously in similar structures.

Subcomponent self‐assembly of a cyclic tetranuclear Fe(II) helicate in a highly diastereoselective self‐sorting manner

Abstract An enantiomerically pure diamine based on the 4,15‐difunctionalized [2.2]paracyclophane scaffold and 2‐formylpyridine self‐assemble into an optically pure cyclic metallosupramolecular Fe4L6 helicate upon mixing with iron(II) ions in a diastereoselective subcomponent self‐assembly process. The cyclic assembly results from steric strain that prevents the formation of a smaller linear dinuclear triple‐stranded helicate, and hence, leads to the larger strain‐free assembly that fulfils the maximum occupancy rule. Interestingly, use of the racemic diamine also leads to a racemic mixture of the homochiral cyclic helicates as the major product in a highly diastereoselective narcissistic ch…

Two (E)-2-({[4-(dialkylamino)phenyl]- imino}methyl)-4-nitrophenols

The slow evaporation of analytical NMR samples resulted in the formation of crystals of (E)-2-({[4-(dimethyl­amino)­phenyl]­imino}­methyl)-4-nitro­phenol, C15H15N3O3, (I), and (E)-2-({[4-(diethyl­amino)­phenyl]­imino}­methyl)-4-nitrophenol, C17H19N3O3, (II). Despite the small structural difference between these two N-salicylidene­aniline derivatives, they show different space groups and diverse mol­ecular packing. The mol­ecules of both compounds are close to being planar due to an intra­molecular O-H...N hydrogen bond. The 4-alkyl­amino-substituted benzene ring is inclined at an angle of 13.44 (19)° in (I) and 2.57 (8)° in (II) with respect to the 4-nitro-substituted phenol ring. Only very…

Dimensionality Variation in Polymeric Metallo‐Organic Frameworks

Single crystal X-ray crystallography was used to determine the structures of four metallo-organic complexes derived from pyridyl ligands and the metal ions, Cu2+, Zn2+ and Ag+. Two metallo-organic layer framework structures (1 and 3), a strand (2) and a dimer (4) structure were formed when the tetradentate ligands, tetrakis(nicotinoxymethyl)methane (TNM) and tetrakis(isonicotinoxymethyl)methane (TINM), were reacted with the first and second row transition metal cations, copper, silver, and zinc. The choice of anion and ligand was found to affect the outcome of the structure. Contrary to our previous results with the same ligands and similar transition metal cations, no genuine 3D metallo-or…

Crystallography and Crystal Engineering

The C–I･･･⁻O–N⁺ Halogen Bonds with Tetraiodoethylene and Aromatic N-oxides

The nature of C–I⋯⁻O–N⁺ interactions, first of its kind, between non-fluorinated tetraiodoethylene XB-donor and pyridine N-oxides (PyNO) are studied by single-crystal X-ray diffraction (SCXRD) and Density Functional Theory (DFT) calculations. Despite the non-fluorinated nature of the C2I4, the I⋯O halogen bond distances are similar to well-known perfluorohaloalkane/-arene donor-PyNO analogues. With C2I4, oxygens of the N-oxides adopt exclusively 2-XB-coordination in contrast to the versatile bonding modes observed with perfluorinated XB-donors. The C2I4 as the XB donor forms with PyNO’s one-dimensional chain polymer structures in which the C2I4⋯(μ-PyNO)2⋯C2I4 segments manifesting two bondin…

Bringing a Molecular Plus One : Synergistic Binding Creates Guest-Mediated Three-Component Complexes

C-Ethyl-2-Methylresorcinarene (A), pyridine (B), and a set of ten carboxylic acids (Cn) associate to form A·B·Cn ternary assemblies with 1:1:1 stoichiometry, representing a useful class of ternary systems where the guest mediates complex formation between the host and a third component. Although individually weak in solution, the combined strength of the multiple non-covalent interactions organizes the complexes even in a highly hydrogen-bond competing methanol solution as explored by both experimental and computational methods. The interactions be-tween A·B and Cn are dependent on the pKa values of carboxylic acids. The weak interactions between A and C further reinforce the interactions b…

Wasserstoffbrücken-gebundene Analoga von Cavitanden

Squaramide-Catalyzed Asymmetric aza-Friedel-Crafts/N,O-Acetalization Domino Reactions Between 2-Naphthols and Pyrazolinone Ketimines

N-Boc ketimines derived from pyrazolin-5-ones were explored to develop an unprecedented domino aza-Friedel-Crafts/N,O-acetalization reaction with 2-naphthols. The novel method requires a catalyst loading of only 0.5 mol % of a bifunctional squaramide catalyst, is scalable to gram amounts, and provides a new series of furanonaphthopyrazolidinone derivatives bearing two vicinal tetra-substituted stereogenic centers in excellent yields (95-98 %) and stereoselectivity (>99:1 d.r. and 97-98 % ee). A different reactivity was observed in the case of 1-naphthols and other electron-rich phenols, which led to the aza-Friedel-Crafts adducts in 70-98 % yield and 47-98 % ee.

The complex formation of tetracyclohexylammonium C1-resorcinarene with various guests - an electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry study.

The complex formation of a tetraammonium C1-resorcinarene (R+4HCl) was studied using electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Although R+4HCl easily loses its counter ions in the ESI process, a neutral self-assembled structure with an intramolecular circular hydrogen-bonded 16-membered -N(+)-H ... X(-) ... H-N(+)- array with ammonium ion as the charge-giving species was observed in the gas phase. In addition to chloride, several other counter ions were also studied. The size and basicity of the counter ion as well as the size of the charge-giving cation strongly affected the gas-phase stability of the self-assembled system. H/D exchang…

Self-assembly of 1- and 2-Dimensional Multicompartmental Arrays via the 2-Aminopyrimidine H-Bonding Motif and Selective Guest Inclusion

Abstract The H-bond mediated self-assembly of aminopyrimidine substituted anthracene derivatives 4 and 5, respectively, generate 1- and 2-dimensional multicompartmental arrays in the solid state as revealed by X-ray crystallographic analysis. The derived ‘pigeon-hole’ lattice is defined by syn-coplanar positioning of anthracene moieties at a distance of ca. 7 A, allowing the formation of selective clathrate-type inclusion entities with guests of appropriate shape and size, in particular phenazine, which presents both structural and interactional complementarity. These data provide insight into the interplay of the different structural and interactional features of the molecular components t…

Unravelling substitution effects on charge transfer characteristics in cocrystals of pyrene based donors and 3,5-dinitrobenzoic acid

Here we report charge-transfer cocrystals composed of pyrene and amino/bromopyrene as π-donors (D) and 3,5-dinitrobenzoic acid (A) as a π-acceptor. The 1 : 1 cocrystals of pyrene/1-aminopyrene adopt a ⋯DADADA⋯ mixed stack arrangement whereas the 2 : 1 cocrystal of 1-bromopyrene and 3,5-dinitrobenzoic acid shows ⋯DDADDA⋯ stacking. Crystallographic, spectral and theoretical studies reveal that the frontier molecular orbital energy level rather than the π-donor strength plays the governing role in predicting charge transfer. In addition, a theoretical study demonstrates that the ambipolar semiconductor nature in cocrystals of the pyrene/aminopyrene donor and the p-type nature of bromopyrene wi…

Innentitelbild: A Self-Assembled M8L6 Cubic Cage that Selectively Encapsulates Large Aromatic Guests (Angew. Chem. 15/2011)

Complexation of C-methyl pyrogallarene with small quaternary and tertiary alkyl ammonium cations

Complexation properties of pyrogallarene 1 towards small quaternary and tertiary alkyl ammonium cations were studied in gas phase, solution and in solid state. In gas phase both dimeric capsules and monomeric 1 : 1 complexes of all cations 2a+–d+ are detected but only in the case of 2a+ is the abundance of the capsule form higher than the monomeric 1 : 1 complex. A similar trend is observed in NMR experiments, which reveal a favourable dimeric complex for 2a+ and a weaker dimeric complex for 2b+ but only monomeric complexes for 2c+ and 2d+. Also in solid state, 2a+ and 2b+ form capsules when crystallized from MeOH while 2c+ and 2d+ form dimeric 1 : 1 complexes. As a reference, hetero-confor…

Synthesis, characterization, and thermal behavior of steroidal dendrons

A series of novel dendritic steroidal polyesters of first and second generation has been synthesized in convergent fashion by the use of 2,2-bis(hydroxymethyl)propionic acid as a repeating unit. The first- and second-generation hydroxy-functionalized dendrons with a variety of surface modifications were produced through the use of four bile acids: lithocholic acid (LCA), ursodeoxycholic acid (UDCA), deoxycholic acid (DCA), and cholic acid (CA). The thermal behavior of the steroidal dendrons was characterized by differential scanning calorimetry (DSC) and by thermogravimetric analysis (TGA). Finally, quantum chemical calculation methods were used to study the geometries of the dendrons and t…

Association of 2-acylaminopyridines and benzoic acids. Steric and electronic substituent effect studied by XRD, solution and solid-state NMR and calculations

Abstract Eight single crystal X-ray structures, solid-state NMR spectroscopic, and theoretical studies utilizing QTAIM methodology were used to characterize the 2-acyl (alkyl in acyl = methyl, ethyl, t-butyl, and 1-adamantyl) amino-6-R-pyridine/4-R′-benzoic acid (R,R′ = H or Me) cocrystals. As expected among alkyl groups 1-adamantyl due to its bulkiness has the most significant effect on the relative positions of molecules in cocrystals. In addition, the subtle electronic and steric effects by the methyl substituents were observed. The theoretical calculations with full geometry optimizations are in agreement with the experimental findings (geometry, energy of hydrogen bonds). Based on the …

Dimeric capsules of tetraurea calix[4]arenes. MD simulations and X-ray structure, a comparison

The single crystal X-ray structure of a homodimer of a tetra(tolylurea) calix[4]arene including a tetraethylammonium cation as guest shows an expansion of the capsule and a distortion of its shape, in comparison to the structure of a similar dimer with an encapsulated benzene molecule. Thus, only 8 of 16 possible hydrogen bonds are present in the hydrogen bonded belt holding together the two hemispheres. The encapsulated cation is disordered over two equivalent positions with two methyl groups pointing to the equator, while two methyl groups pointing to the poles form CH–π interactions with the inner surfaces of the calixarene cavities. MD simulations are in agreement with the distorted X-r…

Syntheses and crystal structures of three novel Cu(II) coordination polymers of different dimensionality constructed from Cu(II) carboxylates (carboxylate=malonate (mal), 2 acetate (ac), fumarate (fum)) and conformationally flexible 1,4-bis(imidazole-1-yl-methylene)benzene (IX)

Abstract We herein report three new coordination polymers generated from Cu(II) carboxylates (mal, 2ac, fum) and conformationally flexible bifunctional IX as building blocks. All the three complexes adopt unique structures in the solid state. The complex [Cu2(mal)2(IX)2(H2O)6]n crystallizes as orthorhombic co-linear rods with space group P2(1) P2(1) P2(1). Each rod is further formed of two tightly intertwined strings. The second polymer [Cu2(ac)4(IX)2]n crystallizes with space group P1 which consists of two sets of intersecting 2D sheets composed of parallel rods which interpenetrate to form a fully interlocked 3D structure. In both these complexes IX coordinates in the anti mode. The third…

Weak non-covalent interactions control the relative molecular orientation in the crystals of N-pentafluorobenzyl aniline derivatives

The crystal structures of N-pentafluorobenzyl aniline derivatives are controlled by versatile aromatic–aromatic interactions between the electron deficient and electron rich aromatics; the parent compound (1) possesses an L shape while protonation (2–5) induces a conformational change resulting in a planar arrangement of molecules which pack in layer type structures with different molecular orientations.

DOSY NMR, X-ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M6L4 Coordination Cages.

A novel modular approach to electron-deficient and electron-rich M6L4 cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two C3-symmetric ligands L1 and L2 with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand L1 is more electron-deficient than the well-known 2,4,6-tri(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand L2 is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)Pt(OTf)2] or [(dppp)Pd(OTf)2] corner-complexes yields two electron-deficient (1a and 1b) and two electron-rich …

Syntheses of Trifluoroethylated N-Heterocycles from Vinyl Azides and Togni’s Reagent Involving 1,n-Hydrogen-Atom Transfer Reactions

2,2,2-Trifluoroethyl-substituted 3-oxazolines, 3-thiazolines, and 5,6-dihydro-2H-1,3-oxazines have been obtained by reacting substituted vinyl azides with a combination of Togni’s reagent and substoichiometric amounts of iron(II) chloride. The results of density functional theory calculations support the proposed mechanism involving 1,n-hydrogen-atom transfer reactions. peerReviewed

Base-promoted direct amidation of esters: beyond the current scope and practical applications

The base-promoted direct amidation of unactivated esters is among the most useful reactions for amide bond formation in contemporary organic chemistry. The intensive research in this area has led to the development of a number of new methods to achive this transformation. However, to date, the existing literature is more methodological and in many instances lacks practical directions. Therefore, the full potential of this transformation is yet to be revealed by broadening the substrate scope. In a search for new practical applications of the amidation reaction, herein we present a comprehensive study of a number of base-promoted direct amidations that encompass a wide range of amines and es…

Synthesis of Polycyclic Indolines utilizing a reduction/cyclization cascade reaction

Subsequent reduction and dearomatizing cyclization reactions open up an entry into the synthesis of novel N-fused polycyclic indolines. The dearomatizing cyclization as key step of the sequence proceeds well with Cu(OTf)2 or TfOH as catalyst. At elevated temperature reduction of nitro-substituted precursors with iron under acidic conditions affords a broad variety of polycyclic indolines directly in a two-step cascade reaction in good to excellent yields. Using the developed protocol, the alkaloids Tryptanthrin and Phaitanthrin C have been prepared. peerReviewed

Silver Ion-Selective Electrodes Based on π-Coordinating Ionophores Without Heteroatoms

Ion-selective electrodes (ISEs) were constructed by using spherical hydrocarbons (cyclophanes) as π-coordinating ionophores in solvent polymeric membranes. Four structurally similar cyclophanes, i. e., [2.2.2]p,p,p-cyclophane, [2.2.2]m,p,p-cyclophane, [2.2.1]p,p,p-cyclophane and [2.2.1]m,p,p-cyclophane were studied as ionophores for Ag+. The ion-selective membranes were composed of the corresponding ionophore (1%), potassium tetrakis(4-chlorophenyl)borate (0.5%), 2-nitrophenyl octyl ether (65–66%) and PVC (32–33%). The ion-selective membrane was placed on top of a layer of the conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), working as ion-to-electron transducer. The selectivit…

Synthesis of N‐Monosubstituted Sulfondiimines by Metal‐free Iminations of Sulfiliminium Salts

Sulfondiimines are marginalized entities among nitrogencontaining organosulfur compounds, despite offering promising properties for applications in various fields including medicinal and agrochemical. Herein, we present a metal-free and rapid synthetic procedure for the synthesis of N-monosubstituted sulfondiimines that overcomes current limitations in their synthetic accessibility. Particularly, S,S-dialkyl substrates, which are commonly difficult to convert by existing methods, react well with a combination of iodine, 1,8-diazabicyclo[5.4.0]undec-7-en (DBU), and iminoiodanes (PhINR) in acetonitrile (MeCN) to furnish the corresponding sulfondiimines in yields up to 85% (25 examples). Valua…

Mannich Reactions with Amino Alcohols

The condensation of resorcarenes 1 with various amino alcohols and an excess of formaldehyde was studied. The tetrabenzoxazines 2a−e were found as the only products in the reaction with 6-aminohexan-1-ol, 4-aminobutan-1-ol, and 2-aminoethanol, while 3-aminopropan-1-ol forms the tetraoxazine 3 as the main product. In the case of aminoethanols substituted at the 2-position with alkyl groups, the tetraoxazolidines 4 are the preferred reaction products, while 1-methyl aminoethanol (1-amino-propan-2-ol) yields predominantly the tetrabenzoxazine 2f. The structures of all these compounds have been confirmed by NMR spectroscopy and additionally by single-crystal X-ray analysis in the case of 2a and…

Exploring the 2,2′-Diamino-5,5′-bipyrimidine Hydrogen-Bonding Motif: A Modular Approach to Alkoxy-Functionalized Hydrogen-Bonded Networks

The programmed self-association of 2,2’-diamino-4,4’-dialkoxy-5,5’-bipyrimidines allows for the de novo construction of alkoxy-functionalized H-bonded ribbons and sheets as evidenced by X-ray crystallographic analysis. The data provide insight into the interplay of the different structural and interactional features of the molecular components to the generation of the supramolecular assembly. Hydrophobicity of the didodecyl side chains of 4c leads to the dominance of the H-bonding factor, resulting in the formation of a fully interconnected array. These results define the utility of the of 2,2’-diamino-4,4’-dialkoxy-5,5’-bipyrimidines as a potential scaffold for the attachment of electro- o…

The Halide Binding Behavior of 2-Carbamoyl-7-ureido-1H-indoles: Conformational Aspects

Indole-based anion receptors with an carboxamide unit in 2- and an urea in 7-position were prepared and found to bind halides (as well as acetate and nitrate) in chloroform solutions at room temperature. Investigations of the binding behaviour show that the receptor is selective for chloride. Surprisingly, the truncated receptor 3 without the 2-carbamoyl substituent shows the highest affinity for Cl–. Thorough 1H, 13C and 15N NMR investigations indicate different binding modes for acetate, nitrate and halides to the receptor 2. The observation of a major conformational change of this receptor during the binding of the halide ions leads to an understanding of the relative binding affinities …

Halogen bonding—a key step in charge recombination of the dye-sensitized solar cell

The halogen bonding between [Ru(dcbpy)(2)(SCN)(2)] dye and I(2) molecule has been studied. The ruthenium complex forms a stable [Ru(dcbpy)(2)(SCN)(2)]···I(2)·4(CH(3)OH) adduct via S···I interaction between the thiocyanate ligand and the I(2) molecule. The adduct can be seen as a model for one of the key intermediates in the regeneration cycle of the oxidized dye by the I(-)/I(3)(-) electrolyte in dye sensitized solar cells.

Self-assembly of janus dendrimers into uniform dendrimersomes and other complex architectures

Janus Drug Delivery Vehicle Efficient drug delivery vehicles need to be produced in a limited size range and with uniform size distribution. The self-assembly of traditional small-molecule and polymeric amphiphiles has led to the production of micelles, liposomes, polymeric micelles, and polymersomes for use in drug delivery applications. Now, Percec et al. (p. 1009 ) describe the self-assembly of Janus-type (i.e., two-headed) dendrimers to produce monodisperse supramolecular constructs, termed “dendrimersomes,” and other complex architectures. The structures, which showed long-term stability as well as very narrow size distributions, were easily produced by the injection of an ethanolic so…

Cooperative Assistance in Bifunctional Organocatalysis: Enantioselective Mannich Reactions with Aliphatic and Aromatic Imines

both of which contain a thiourea moiety (Scheme 1).The catalysts are capable of deprotonating suitable nucleo-philes, such as activated carbonyl compounds. This proton-transfer reaction generates an ion pair, which is composed ofthe protonated catalyst and the anionic nucleophile interact-ing through hydrogen bonds. At least one of the NH moietiesin the protonated catalyst is involved in activating theelectrophilic reaction partner.

A Double Calix[4]arene in a 1,3-alternate Conformation

N-Heterocyclic Carbene Catalyzed Asymmetric Synthesis of Dihydropyranothiazoles­ via Azolium Enolate Intermediates

A highly diastereo- and enantiostereoselective synthesis of bicyclic dihydropyranothiazoles combining a thiazole and δ-lactone skeleton via NHC-catalyzed [4+2] annulation of 5-alkenylthiazolones and α-chloroaldehydes has been developed. The heterocyclic products are formed via azolium enolate intermediates in good yields with high diastereo- and enantistereoselectivities.

Guest-Induced Folding and Self-Assembly of Conformationally Adaptive Macrocycles into Nanosheets and Nanotubes

A conformationally adaptive macrocycle is presented, namely zorb[4]arene, which exists in multiple conformations in the uncomplexed state. The binding cavity of zorb[4]arene is concealed, either due to a collapsed conformation or by self-inclusion. The zorb[4]arene with long alkyl chains manifests itself with surprisingly low melting point and thus exist as an oil at room temperature. Binding of a guest molecule induces the folding and conformational rigidity of zorb[4]arene and leads to well-defined three-dimensional structures, which can further self-assemble into nanosheets or nanotubes upon solvent evaporation, depending on guest molecules and the conformations they can induce.

Host-guest complexes of C-propyl-2-bromoresorcinarene with aromatic N-oxides*

The host-guest complexes of C-propyl-2-bromoresorcinarene with pyridine N-oxide, 3-methylpyridine N-oxide, quinoline N-oxide and isoquinoline N-oxide are studied using single crystal X-ray crystallography and 1H NMR spectroscopy. The C-propyl-2-bromoresorcinarene forms endo-complexes with the aromatic N-oxides in the solid-state when crystallised from either methanol or acetone. In solution, the endo-complexes were observed only in methanol-d4. In DMSO the solvent itself is a good guest, and crystallisation provides only solvate endo-complexes. The C-propyl-2-bromoresorcinarene shows remarkable flexibility when crystallised from either methanol or acetone, and packs into one-dimensional sel…

Synthesis and thermal behavior of Janus dendrimers, part 1

Abstract Eight Janus-type dendrimers up to the second generation were synthesized, and their thermal properties were evaluated. Compounds consist of the dendritic bisMPA based polyester moieties, and either 3,4-dihexyloxybenzoic acid or 3,4-dihexadecyloxybenzoic acid moieties, attached to opposite sides of the pentaerythritol core. The structures of the molecules were verified with 1 H NMR, 13 C NMR, ESI TOF mass spectrometry and elemental analysis. The thermal stability was evaluated by thermogravimetric analysis, displaying onset decomposition temperatures ( T d ) ranging from 241 to 308 °C. Phase transitions were studied by differential scanning calorimetry. Based on the performed studie…

Cover Feature: Synthesis of Polycyclic Indolines by Utilizing a Reduction/Cyclization Cascade Reaction (Eur. J. Org. Chem. 45/2021)

Selective recognition of small hydrogen bond acceptors by a calix[6]arene-based molecular container

Selective molecular recognition is of primary importance for applications such as sensing and separation of chemicals. This work describes the host-guest and crystallisation properties of a penta-carbamated calix[6]arene designed as a molecular container with a H-donating recognition group directed towards the heart of the cavity. As demonstrated by NMR spectroscopy and X-ray diffraction studies, this macrocyclic receptor can selectively recognise small H-bond acceptors through one or two hydrogen bonds, the guests nesting inside the polyaromatic cavity surrounded by eleven bulky tert-butyl groups.

A linear Fe-O-Fe unit in bis(dibenzyldimethylammonium) mu-oxo-bis[tribromoferrate(III)].

The title compound, (C 16 H 20 )N) 2 [Fe 2 Br 6 O], crystallizes with one dibenzyldimethylammonium cation and one half of a μ-oxo-bis[tribromoferrate(III)] anion in the asymmetric unit. The bridging oxo group is situated on an inversion centre, resulting in a linear conformation for the Fe-O-Fe unit. The iron(III) cations have tetrahedral geometry, with bond angles in the range 106.8 (1)-112.2 (1)°. The ion pairs are held together by Coulombic forces and C-H···Br hydrogen bonds. Each Br - anion forms one hydrogen bond. No C-H···O hydrogen bonds are found between the O atom in the Fe-O-Fe unit and surrounding counter-cations, consistent with the linear configuration of the Fe-O-Fe unit.

Asymmetric Synthesis of Tetrahydrobenzofurans and Annulated Dihydropyrans via Cooperative One-Pot Organo- and Silver-Catalysis

Synthesis : journal of synthetic organic chemistry 48(19), 3207-3216(2016). doi:10.1055/s-0035-1561468

Heads or Tails? Sandwich-Type Metallo Complexes of Hexakis(2,3-di-O-methyl)-α-cyclodextrin

Native and synthetically modified cyclodextrins (CDs) are useful building blocks in the construction of large coordination complexes and porous materials with various applications. Sandwich-type co...

Single and Multiple Additions of Dibenzoylmethane onto Buckminsterfullerene (Eur. J. Org. Chem. 35/2013)

Definition of the halogen bond (IUPAC Recommendations 2013)

This recommendation proposes a definition for the term “halogen bond”, which designates a specific subset of the inter- and intramolecular interactions involving a halogen atom in a molecular entity.

Endo-/exo- and halogen-bonded complexes of conformationally rigid C-ethyl-2-bromoresorcinarene and aromatic N-oxides

The host-guest complexes of conformationally rigid C-ethyl-2-bromoresorcinarene with aromatic N-oxides were studied using single crystal X-ray crystallography. Unlike that of the conformationally more flexible C-ethyl-2-methylresorcinarene, the C-ethyl-2-bromoresorcinarene cavity forms endo-complexes only with the small pyridine-N-oxides, such as pyridine N-oxide, 2-methyl-, 3-methyl- and 4-methylpyrdine N-oxide, and quinoline N-oxide. The larger 2,4,6-trimethylpyridine, 4-phenylpyridine and isoquinoline N-oxide, and 4,4-bipyridine N,N′-dioxide and 1,3-bis(4-pyridyl)propane N,N′-dioxide do not fit into the host cavity. Instead endo-acetone complexes are formed. Remarkably, differing from th…

Organocatalytic Domino Oxa-Michael/1,6-Addition Reactions: Asymmetric Synthesis of Chromans Bearing Oxindole Scaffolds.

An asymmetric organocatalytic domino oxa-Michael/1,6-addition reaction of ortho-hydroxyphenyl-substituted para-quinone methides and isatin-derived enoates has been developed. In the presence of 5 mol % of a bifunctional thiourea organocatalyst, this scalable domino reaction affords 4-phenyl-substituted chromans bearing spiro-connected oxindole scaffolds and three adjacent stereogenic centers in good to excellent yields (up to 98 %) and with very high stereoselectivities (up to >20:1 d.r., >99 % ee).

Chiroptical inversion of a planar chiral redox-switchable rotaxane.

Reversible redox-switching of a planar chiral [2]rotaxane with a tetrathiafulvalene-bearing crown ether macrocycle generates a complete sign reversal of the main band in the ECD spectrum, as shown by experiment and rationalised by DFT calculations.

Recognition of oxovanadium(V) species and its separation from other metal species through selective complexation by some acyclic ligands

Acyclic molecules possessing –OH (phenoxo and alkoxo type) groups and imine or amine moieties have been developed to sense the specific preference for VO3+ species. These molecules also showed a capability to quantitatively separate oxovanadium(V) species from a reaction mixture containing metal species of V, Mo, U, Fe, and Mn ions in solution. A cascade quantitative separation of VO3+ followed by cis–MoO2+2 followed by trans –UO2+2 species is demonstrated from their mixture. Synthesis and structural details of oxo-species of vanadium molybdenum and uranium are also discussed. Factors influencing the complexation of these molecules towards oxo metal species of V, Mo and U are also addressed.

Tridentate C–I⋯O−–N+ halogen bonds

The X-ray structures of the first co-crystals where the three oxygen lone pairs in N-oxides are fully utilized for tridentate C–I⋯O−–N+ halogen bonding with 1,ω-diiodoperfluoroalkanes are reported, studied computationally, and compared with the corresponding silver(I) N-oxide complexes. peerReviewed

First Crystallographic Investigation of Complexes of cis-VO2+, cis-MoO22+, and trans-UO22+ Species with Schiff-Base Molecules Derived from 4,6-O-Ethylidene-β-D-glucopyranosylamine

The interaction of Schiff-base ligands derived from 4,6-O-ethylidene-β-D-glucopyranosylamine with cis-VO 2 + , cis-MoO 2 2+ , and trans-UO 2 2+ species have been studied by isolating and characterizing the corresponding products. The structures of one complex of each type of species have been established by single-crystal X-ray diffraction analysis. In all the complexes, the saccharide moiety adopts a chair conformation and has a β-anomeric form. A gradual increase in coordination number (5, 6, and 7) and a gradual variation in the geometry (distorted trigonal-bipyramidal, distorted octahedral, and pentagonal-bipyramidal) are observed on going from the complexes of cis-VO 2 + (mononuclear) …

ChemInform Abstract: Cooperative Assistance in Bifunctional Organocatalysis: Enantioselective Mannich Reactions with Aliphatic and Aromatic Imines.

both of which contain a thiourea moiety (Scheme 1).The catalysts are capable of deprotonating suitable nucleo-philes, such as activated carbonyl compounds. This proton-transfer reaction generates an ion pair, which is composed ofthe protonated catalyst and the anionic nucleophile interact-ing through hydrogen bonds. At least one of the NH moietiesin the protonated catalyst is involved in activating theelectrophilic reaction partner.

Efficient Self-Assembly of Di-, Tri-, Tetra-, and Hexavalent Hosts with Predefined Geometries for the Investigation of Multivalency

Coordination-driven self-assembly of differently shaped di- to hexavalent crown-ether host molecules is described. A series of [21]crown-7- and [24]crown-8-substituted bipyridine and terpyridine ligands was synthetized in a "toolbox" approach. Subsequent coordination to 3d transition metal and ruthenium(II) ions provides an easy and fast access to host assemblies with variable valency and pre-defined orientations of the crown-ether moieties. Preliminary isothermal calorimetry (ITC) titrations provided promising results, which indicated the host complexes under study to be suitable for the future investigation of multivalent and cooperative binding. The hosts described herein will also be su…

Systematic Construction of Ternary Cocrystals by Orthogonal and Robust Hydrogen and Halogen Bonds

A carefully designed strategy is presented for the construction of ternary cocrystals, based on the orthogonality of two supramolecular interaction modes: hydrogen bonding between crown ethers and thioureas and the halogen bonding between thioureas and perfluorohalocarbons. Tested on a set comprising two crown ethers, two thioureas and five halogen bond donors, the strategy resulted in a high, 75% success rate, with 15/20 component combinations yielding at least one cocrystal. Crystal structure analysis revealed the interplay between the hydrogen and halogen bonding motifs, also shedding light on the variables affecting their formation. peerReviewed

Encapsulation of tetramethylphosphonium cations

International audience; The weak interactions and capsule formation of tetramethylphosphonium (TMP) cation with resorcinarenes 1 and 2 and the corresponding pyrogallarenes 3 and 4 were studied in the solid state by single crystal X-ray diffraction, in solution by NMR and in the gas phase by mass spectrometry. In methanol-D4, the NMR titration studies reveal that the association constants for the 1:1 complexes of TMP@3 and TMP@4 are much higher (TMP@4:390±37 M-1) than for the corresponding TMP@1 and TMP@2 (TMP@2:130±10 M-1) complexes. In the gas phase both monomeric 1:1 TMP@1-TMP@4 complexes as well as the dimeric 1:2 capsule complexes, TMP@12-TMP@42 were observed. The 1:1:2 molar mixtures o…

Synthesis and Coordination Chemistry of Lower Rim Cavitand Ligands

Aromatic N-oxide templates open inclusion and dimeric capsular assemblies with methylresorcinarene

C2-2-methylresorcinarene forms host–guest complexes with pyridine N-oxide and quinoline N-oxide. In solution the NMR studies support the 1 : 1 host–guest complexes while in the solid state, the single crystal X-ray diffraction studies reveal dimeric capsule-like assemblies with 2 : 3 and 2 : 2 host–guest stoichiometry.

Crystal Structures and Thermal Behavior of Isostructural Bis(dibenzyldimethylammonium) Tetrachlorometallate [M = Mn(II), Co(II), Ni(II) and Zn(II)] Solvates Crystallized from Acetonitrile and/or Methanol Solutions

Five isostructural bis(dibenzyldimethylammonium) tetrachlorometallate solvate complexes [M = Mn(II), Co(II), Ni(II) or Zn(II)] were crystallized from acetonitrile and/or methanol solutions. The crystal structures are compared to those of the analogous, isostructural copper compounds (X = Cl or Br) reported earlier. The complexes crystallize in the monoclinic space group P21/n with Z = 4, and unit cell dimensions of a ≈ 14.1, b ≈ 16.1, c ≈ 15.7 °A and β ≈ 108 - 109°. The asymmetric unit of these compounds contains one MCl4 2− anion, two Bz2Me2N+ cations in theW-conformation and one half of a disordered solvent molecule (acetonitrile or methanol). The geometry of the MCl4 2− anion is close to…

Mn(IV) and Co(III)-complexes of –OH-rich ligands possessing O2N, O3N and O4N cores: syntheses, characterization and crystal structures

Mn(IV) and Co(III) complexes of tridentate –OH–rich ligands possessing O2N, O3N and O4N donor sets were synthesized, characterized and their structures were established by single crystal X-ray diffraction, where the binding core is O4N2. In the structurally characterized complexes, the coordination geometry about the metal ion was found to be distorted octahedral.

Non-Centrosymmetric Tetrameric Assemblies of Tetramethylammonium Halides with Uranyl Salophen Complexes in the Solid State

Ditopic salophen-UO(2) receptors 1-4 and 7 co-crystallize with tetramethylammonium (TMA) chloride and fluoride salts producing good quality crystals amenable for X-ray diffraction characterization. The arrangement of the receptor and salt units in the crystal lattice is such that tetrameric ball-shaped assemblies are formed, where an inner cluster of four TMA cations are surrounded by an outer shell of four UO(2)-bound anions. These elaborate architectures, which occur in all cases, regardless of a certain degree of structural modification on the receptors, lead to lattices that belong to non-centrosymmetric (NCS) space groups. Interestingly, the tetragonal symmetry of the tetrameric ball-s…

Four-, five- and six-coordinated Zn-II complexes of OH-containing ligands: Syntheses, structure and reactivity

Four-, five- and six-coordinated complexes of Zn-II with OH-rich molecules possessing an ONO binding core were synthesized, characterized and their structures were established by single-crystal X-ray diffraction, The corresponding metal ion geometries were found to be distorted tetrahedral, square pyramidal and octahedral, respectively. The complexes exhibit interesting lattice structures such as layered and corrugated sheets owing to the presence of a number of weak intermolecular interactions. The five-coordinated, water-bound Zn-II complex was studied because of its putative hydrolysis property towards p-nitrophenyl acetate. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.

An Octanuclear Metallosupramolecular Cage Designed To Exhibit Spin-Crossover Behavior.

By employing the subcomponent self-assembly approach utilizing 5,10,15,20-tetrakis(4-aminophenyl)porphyrin or its zinc(II) complex, 1H-4-imidazolecarbaldehyde, and either zinc(II) or iron(II) salts, we were able to prepare O-symmetric cages having a confined volume of ca. 1300 Å3 . The use of iron(II) salts yielded coordination cages in the high-spin state at room temperature, manifesting spin-crossover in solution at low temperatures, whereas corresponding zinc(II) salts led to the corresponding diamagnetic analogues. The new cages were characterized by synchrotron X-ray crystallography, high-resolution mass spectrometry, and NMR, Mössbauer, IR, and UV/Vis spectroscopy. The cage structures…

N-(2,3,5,6-Tetrafluoropyridyl)sulfoximines : synthesis, X-ray crystallography, and halogen bonding

In the presence of KOH, NH-sulfoximines react with pentafluoropyridine to give N-(tetrafluoropyridyl)sulfoximines (NTFP-sulfoximines) in moderate to excellent yields. Either a solution-based or a superior solvent-free mechanochemical protocol can be followed. X-Ray diffraction analyses of 26 products provided insight into the bond parameters and conformational rigidity of the molecular scaffold. In solid-state structures, sulfoximines with halo substituents on the S-bound arene are intermolecularly linked by C–X⋯O[double bond, length as m-dash]S (X = Cl, Br) halogen bonds. Hirshfeld surface analysis is used to assess the type of non-covalent contacts present in molecules. For mixtures of th…

Synthese und Struktur eines durch Multikomponenten-Selbstorganisation erhaltenen dreikernigen [4]Pseudorotaxans

Halogen Bonding Based “Catch and Release”: Reversible Solid State Entrapment of Elemental Iodine with Mono-Alkylated DABCO Salts

The halogen bonding (XB) between elemental iodine (I2) and neutral 1,4-diazabicyclo[2.2.2]octane (DABCO) and its monoalkylated PF6– salts was studied by X-ray crystallographic, thermoanalytical, and computational methods. DABCO was found to form both 1:1 and 1:2 complexes with I2 showing an exceptionally strong halogen bond (ΔEcp = −73.0 kJ/mol) with extremely short N···I distance (2.37 A) in the 1:1 complex (1a). In the more favored 1:2 complex (1b), the XB interaction was found to be slightly weaker [ΔEcp = −64.4 kJ/mol and d(N···I) = 2.42 A] as compared to 1a. The monoalkylated DABCO salts (2PF6–7PF6) form corresponding 1:1 XB complexes with I2 {[2···I2]PF6–([7···I2]PF6} similarly to the…

Iodonium complexes of the tertiary amines quinuclidine and 1-ethylpiperidine

Iodonium complexes incorporating tertiary amines have been synthesised to study and explore why such species comprised of alkyl amines are relatively rare. The complexes were characterised in solution (1H and 15N NMR spectroscopy) and the solid state (SCXRD), and analysed computationally. peerReviewed

Influencing the self‐sorting behavior of [2.2]paracyclophane based ligands by introducing isostructural binding motifs

Two isostructural ligands with either nitrile ( L nit ) or isonitrile ( L iso ) moieties directly connected to a [2.2]paracyclophane backbone with pseudo‐meta substitution pattern have been synthesized. The ligand itself ( L nit ) or its precursors ( L iso ) were resolved via HPLC on a chiral stationary phase and the absolute configuration of the isolated enantiomers was assigned by XRD analysis and/or by comparison of quantum‐chemical simulated and experimental ECD‐spectra. Surprisingly, the resulting metallosupramolecular aggregates formed in solution upon coordination of [(dppp)Pd(OTf) 2 ] differ in their composition: whereas L nit forms dinuclear complexes L iso exclusively forms trinuc…

Carbon’s Three-Center-Four-Electron Tetrel Bond, Treated Experimentally

Tetrel bonding is the noncovalent interaction of group IV elements with electron donors. It is a weak, directional interaction that resembles hydrogen and halogen bonding yet remains barely explored. Herein, we present an experimental investigation of the carbon-centered, three-center, four-electron tetrel bond, [N−C− N]+ , formed by capturing a carbenium ion with a bidentate Lewis base. NMRspectroscopic, titration-calorimetric, and reaction-kinetic evidence for the existence and structure of this species is reported. The studied interaction is by far the strongest tetrel bond reported so far and is discussed in comparison with the analogous halogen bond. The necessity of the involvement of…

Utility of Three-Coordinate Silver Complexes Toward the Formation of Iodonium Ions

The work herein describes the synthesis of five three-coordinate silver(I) complexes comprising a bidentate ligand L1, either bpy (2,2′-bipyridyl) or bpyMe2 (4,4′-dimethyl-2,2′-dipyridyl), and a monodentate ligand L2, either mtz (1-methyl-1H-1,2,3-triazole), 4-Etpy (4-ethylpyridine), or 4-DMAP (N,N-dimethylpyridin-4-amine). Upon reaction of the three-coordinate silver(I) complexes with 0.5 equiv of I2, the reactions quantitatively produce a 1:1 pair of complexes of a four-coordinate silver(I) complex [Ag(L1)2]PF6 and a two-coordinate iodonium complex [I(L2)2]PF6. The combination of [Ag(bpyMe2)2]PF6 and [I(4-DMAP)2]PF6 gave rise to an I+···Ag+ interaction where the I+ acts as a nucleophile, …

Organocatalytic Oxa-Michael/Michael/Michael/Aldol Condensation Quadruple Domino Sequence : Asymmetric Synthesis of Tricyclic Chromanes

An efficient and highly stereoselective one-pot, four-component synthesis of functionalized tricyclic chromanes has been achieved through an organocatalyzed quadruple domino reaction. The reaction sequence involves an oxa-Michael/Michael/Michael/aldol condensation between alcohols, 2 equiv of acrolein, and nitrochromenes to generate the pharmaceutically important tricyclic chromanes bearing three contiguous stereogenic centers including a chiral tetrasubstituted carbon center in good domino yields (30–70%) and excellent diastereo- and enantioselectivities (>20:1 dr and >99% ee). peerReviewed

A Bis‐Acridinium Macrocycle as Multi‐Responsive Receptor and Selective Phase‐Transfer Agent of Perylene

A bis‐acridinium cyclophane incorporating switchable acridinium moieties linked by a 3,5‐dipyridylanisole spacer was studied as a multi‐responsive host for polycyclic aromatic hydrocarbon guests. Complexation of perylene was proven to be the most effective and was characterized in particular by a charge transfer band as signal output. Effective catch and release of the guest was triggered by both chemical (proton/hydroxide) and redox stimuli. Moreover, the dicationic host was also easily switched between organic and perfluorocarbon phases for application related to the enrichment of perylene from a mixture of polycyclic aromatic hydrocarbons. peerReviewed

Chloride–hydrogen interactions of picolinic, nicotinic and isonicotinic acid chloride hydrochlorides in the crystalline state

The crystal structures of the three isomers of the chemically labile pyridinecarboxylic acid chloride hydrochlorides were analyzed in order to study the weak interactions of the chloride anion with hydrogens. The chloride anions in the crystal structure of 1a have a slightly distorted square-planar interaction sphere with four hydrogens in the equatorial plane (plane of the molecule) with Cl−⋯H distances varying from 2.041(1) A [NH+⋯Cl−] to 2.933(1) A [CH⋯Cl−]. Nicotinic and isonicotinic acid chloride hydrochloride 1b and 1c show that chloride anion has a crucial role in the formation of bridged dimeric structures. The crystal lattices of 1b and 1c manifest similar herring-bone packing patt…

ChemInform Abstract: Exploring the 2,2′-Diamino-5,5′-bipyrimidine Hydrogen-Bonding Motif: A Modular Approach to Alkoxy-Functionalized Hydrogen-Bonded Networks.

The programmed self-association of 2,2’-diamino-4,4’-dialkoxy-5,5’-bipyrimidines allows for the de novo construction of alkoxy-functionalized H-bonded ribbons and sheets as evidenced by X-ray crystallographic analysis. The data provide insight into the interplay of the different structural and interactional features of the molecular components to the generation of the supramolecular assembly. Hydrophobicity of the didodecyl side chains of 4c leads to the dominance of the H-bonding factor, resulting in the formation of a fully interconnected array. These results define the utility of the of 2,2’-diamino-4,4’-dialkoxy-5,5’-bipyrimidines as a potential scaffold for the attachment of electro- o…

Concave macrobicycles: Absorption spectra, luminescence properties, and endocavital complexation of neutral organic guests

By a mild modified Eglinton coupling a series of diynebridged macrobicyclic hosts capable of endocavital complexation were synthesized and their structures and complexation properties investigated by X-ray analysis. The inclusion of DMSO in 7 suggests a direct correlation between steric fit and orientation of the guest. On the basis of this hypothesis, the orientation of acetone in an endocavital inclusion of 2 was predicted and verified by X-ray analysis. Comparison of the single-crystal X-ray structures of the vacant macrobicycle 3 and of a family of macrobicycles showing endocavital or “pocket” complexation of neutral organic guests suggests that torsion of the cavities upon complexation…

Chiral carbonyl hypoiodites

Three chiral carbonyl hypoiodites, R–C(O)OI, have been prepared from N-protected (S)-valine to give the ligand-stabilised (S)-valinoyl hypoiodite complexes with 4-dimethylaminopyridine, 4-pyrrolidinopyridine, and 4-morpholinopyridine as the stabilising ligands. The identity of the complexes was established by NMR (1H, 13C, 1H–15N HMBC) and single crystal X-ray diffraction analysis. peerReviewed

Halogen Bonds in Square Planar 2,5-Dihalopyridine-Copper(II) Bromide Complexes

Halogen bonding in self-complementary 1:2 metal–ligand complexes obtained from copper(II) bromide (CuBr2) and seven 2,5-dihalopyridines were analyzed using single-crystal X-ray diffraction. All presented discrete complexes form 1D polymeric chains connected with C–X···Br–Cu halogen bonds (XB). In (2-chloro-5-X-pyridine)2·CuBr2 (X = Cl, Br, and I) only the C5-halogen and in (2-bromo-5-X-pyridine)2·CuBr2 (X = Cl, Br, and I) both C2- and C5-halogens form C–X···Br–Cu halogen bonds with the X acting as the XB donor and copper-coordinated bromide as the XB acceptor. The electron-withdrawing C2-chloride in (2-chloro-5-X-pyridine)2·CuBr2 complexes has only a minor effect on the C5–X5···Br–Cu XBs, a…

Multicomponent Self-Assembly: Generation and Crystal Structure of a Trimetallic[4]Pseudorotaxane

Enantioselective synthesis of 4H-pyranonaphthoquinones via sequential squaramide and silver catalysis

Chemical communications 52(8), 1669-1672(2016). doi:10.1039/C5CC09592A

Asymmetric bis-(μ1,1-azido) bridged dinuclear copper(II) complex with N2O donor Schiff base: synthesis, structure and magnetic study

A copper(II) complex, [Cu2(L)2(N3)2] [where HL = 2-((3-(methylamino)propylimino)methyl)-6-methoxyphenol] has been synthesized and characterized by elemental analysis, IR, UV–vis and fluorescence spectroscopy, and single-crystal X-ray diffraction studies. The complex crystallizes in the trigonal space group R. The deprotonated tridentate Schiff base occupies three coordination sites of copper(II). The fourth coordination site is occupied by an azide. A symmetry-related azide from a different molecule coordinates with the fifth site of copper(II), thereby forming a double end-on azide-bridged centrosymmetric dimer. Variable temperature solid–state magnetic studies between 2 and 300 K were car…

Extended Assemblies of Ru(bpy)(CO)2X2 (X = Cl, Br, I) Molecules Linked by 1,4-Diiodotetrafluoro-Benzene (DITFB) Halogen Bond Donors

The ruthenium carbonyl compounds, Ru(bpy)(CO)2X2 (X = Cl, Br or I) act as neutral halogen bond (XB) acceptors when co-crystallized with 1,4-diiodotetrafluoro-benzene (DITFB). The halogen bonding strength of the Ru-X&sdot

Counterion influence on the N–I–N halogen bond

A detailed investigation of the influence of counterions on the [N–I–N]+ halogen bond in solution, in the solid state and in silico is presented. Translational diffusion coefficients indicate close attachment of counterions to the cationic, three-center halogen bond in dichloromethane solution. Isotopic perturbation of equilibrium NMR studies performed on isotopologue mixtures of regioselectively deuterated and nondeuterated analogues of the model system showed that the counterion is incapable of altering the symmetry of the [N–I–N]+ halogen bond. This symmetry remains even in the presence of an unfavorable geometric restraint. A high preference for the symmetric geometry was found also in …

Alternative Motifs for Halogen Bonding (Eur. J. Org. Chem. 9/2013)

Mononuclear Ru(II) PolyPyridyl Water Oxidation Catalysts Decorated with Perfluoroalkyl C 8 H 17 ‐Tag Bearing Chains

Breathing molecular crystals: halogen- and hydrogen-bonded porous molecular crystals with solvent induced adaptation of the nanosized channels

Exceptionally strong (OC–)2N–I⋯N halogen bonding (XB) in a combination with CO⋯H–C hydrogen bonds (HB) between N-iodosuccinimide (NIS) and hexamethylenetetramine (HMTA) yielded a series of molecular crystals possessing large 1D channels. In each structure, HMTA was tetra-coordinated by four NIS molecules resulting in robust [HMTA]·[NIS]4 complexes where the observed I⋯N distances, ranging from 2.486 to 2.586 A, were remarkable shorter (from 29.6 to 26.7%) than the sum of the vdW radii of nitrogen and iodine atoms. Multiple CO⋯H–C HBs interconnected the [HMTA]·[NIS]4 complexes into the structures with flexible “breathing” host-channels. Three different host-channel structures, either oval or…

An all-organic steroid–D–π-A modular design drives ferroelectricity in supramolecular solids and nano-architectures at RT

Confluence of a modular design approach and self-assembly with a 'steroid-D-π-A' module generates spontaneous polarization in solids and for the first time in nano-architectures constituted from organogels, at room temperature (RT).

Dynamic Refolding of Ion-Pair Catalysts in Response to Different Anions.

Four distinct folding patterns were identified in two foldamer-type urea-thiourea catalysts bearing a basic dimethylamino unit by a combination of X-ray crystallography, solution NMR studies, and computational studies (DFT). These patterns are characterized by different intramolecular hydrogen bonding schemes that arise largely from different thiourea conformers. The free base forms of the catalysts are characterized by folds where the intramolecular hydrogen bonds between the urea and the thiourea units remain intact. In contrast, the catalytically relevant salt forms of the catalyst, where the catalyst forms an ion pair with the substrate or substrate analogues, appear in two entirely dif…

Polyester and Ester Functionalized Dendrimers

Demand for smart and functional materials has raised the importance of the research of dendritic (Greek = tree-like) molecules in organic and polymer chemistry due to their novel physical and mechanical properties. The properties of linear polymers as well as small discrete molecules are combined in this new architectural class of macromolecules, that can be divided into two families: dendrimers and hyperbranched macromolecules, that differ in their branching sequences. Dendrimers contain symmetrically arranged branches emanating from a core molecule together with a well-defined number of end groups corresponding to each generation. This results in an almost monodisperse three-dimensional g…

Synthesis, characterization and magnetic study of two new octahedral iron(III) complexes with pendant zwitterionic Schiff bases

Two Schiff bases, HL1 [2-((3-(dimethylamino)propylimino)methyl)-5-bromophenol] and HL2 [2-((2-(diethylamino)ethylimino)methyl)-6-methoxyphenol], have been employed to prepare two new octahedral iron(III) complexes, [Fe(HL1)2(N3)2]ClO4·2H2O (1) and [Fe(HL2)2(NCS)2]ClO4·H2O (2). Both complexes are characterized by spectral and elemental analyses. Single crystal X-ray diffraction studies confirm their structures. In both complexes, Schiff bases are trapped in their zwitterionic forms and coordinated to iron(III) only through the imine nitrogen and phenoxo oxygen, i.e., they behave as bi-dentate ligands, keeping the remaining potential donor sites pendant. The measurement of χM vs. T for both c…

Endo-/Exo- and Halogen Bonded Complexes of Conformationally Rigid Cethyl-2-bromoresorcinarene and aromatic N-oxides

The host–guest complexes of conformationally rigid C-ethyl-2-bromoresorcinarene with aromatic N-oxides were studied using single crystal X-ray crystallography. Unlike that of the conformationally more flexible C-ethyl-2-methylresorcinarene, the C-ethyl-2-bromoresorcinarene cavity forms endo-complexes only with the small pyridine-N-oxides, such as pyridine N-oxide, 2-methyl-, 3-methyl- and 4-methylpyrdine N-oxide, and quinoline N-oxide. The larger 2,4,6-trimethylpyridine, 4-phenylpyridine and isoquinoline N-oxide, and 4,4-bipyridine N,N′-dioxide and 1,3-bis(4-pyridyl)propane N,N′-dioxide do not fit into the host cavity. Instead endo-acetone complexes are formed. Remarkably, differing from th…

Synthesis, crystal and molecular structure of η3-allylundecacarbonylosmium tetrafluoroborate

Abstract The η3-allylundecacarbonylosmium tetrafluoroborate has been synthesized in high yield by treatment of Os3(CO)11MeCN with allyl alcohol and subsequent protonation. It has been studied by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group Pna21 (no. 33) with a 17.933(2), b 11.440(2), c 11.797(2)A and Dc 2.76 g cm−3 for Z = 4. A final R value of 0.046 (Rw = 0.083) based on 2067 reflections was obtained. The presence of the positively charged allyl ligand in the triosmium cluster lengthens the Os1Os2 and Os2Os3 bonds (0.057A) and 0.074 A, respectively) relative to the OsOs bonds in Os3(CO)12.

Experiences with applications of macromolecular tools in supramolecular crystallography

Supramolecular structures, with ever increasing size ranging from a few up to tens of nanometres, represent an intermediate stage between small molecules and biological macromolecules. Many crystal structures of these large supramolecular assemblies have been solved using dual space algorithms. However, supramolecular assemblies with a capsular shape present a particular challenge for crystallography, especially when they are chiral and composed of only light atoms. In this paper, we show that the application of “routine” macromolecular tools may be of great help in solving the crystal structures of supramolecular assemblies that are otherwise refractory to the routine methods of small mole…

Mixed-Valence, Mixed-Spin-State, and Heterometallic [2×2] Grid-type Arrays Based on Heteroditopic Hydrazone Ligands: Synthesis and Electrochemical Features

Une famille de complexes heterometalliques [M 1 2 M 2 2 (L - ) 4 ] n + du type grille [2×2] 1-9 a ete preparee. Les trois approches synthetiques multietapes des ligands hydrazone heteroditopiques A-C possedent chacune des caracteristiques regio-, redox-, enantio-selectives. Ces ligands possedent un groupement NH ionisable et un groupement hydrazone non-ionisable NMe, qui permettent un controle des proprietes redox du metal complexe en fonction de la charge de la cavite coordinante. Les substituants 2-pyrimidine (R) et 6-pyridine (R') influencent de maniere significative la geometrie des complexes formes ainsi que leurs proprietes electrochimiques et magnetiques. Les etudes par spectroscopie…

Specific recognition of fluoride anion using a metallamacrocycle incorporating a uranyl-salen unit

The design and synthesis of a novel fluoride receptor that uses a salen-complexed Lewis acidic uranyl center as the sole binding site is reported here. This receptor binds fluoride anions in DMSO with a high affinity constant (K > 106 M-1) and exhibits a negligible affinity (K < 10 M-1) towards otherwise effective competitors, such as acetate, phosphate and cyanide anions.

Hydrogen and Halogen Bond Mediated Coordination Polymers of Chloro-Substituted Pyrazin-2-Amine Copper(I) Bromide Complexes

A new class of six mono- (1

Ligand entrapment in twofold interpenetrating PtS matrixes by metallo-organic frameworks.

Single-crystal X-ray crystallography was used to determine the structures of four metallo-organic frameworks (MOFs). A dendritic tetradentate ligand (tetrakis(isonicotinoxymethyl)methane, TINM) was used with first-row transition-metal elements copper, nickel, and cobalt to synthesize MOFs with a PtS interpenetration, due to both planar and tetrahedral junctions being present in the framework. Two different polymeric complexes, 1 and 2, were obtained from similar starting materials, TINM and Cu(NO(3))(2).3H(2)O, but different solvents. The use of dichloromethane in addition to methanol and water promoted the coordination of nitrate ions to the copper. With only methanol and water used as sol…

Binding Modes of Nonspherical Anions to N-Alkylammonium Resorcinarenes in the Solid State

A series of hydrogen bond stabilized N-alkylammonium resorcinarene salts with nitrate, triflate, and picrate as the counteranions were synthesized and characterized with 1H NMR and electrospray ionization (ESI) mass spectrometry. Together with electrostatic interactions, the binding of the anions with several hydrogen bond donor sites proceeds through a complex array of intra- and intermolecular hydrogen bonds, evidenced by single crystal X-ray diffraction analysis. These N-alkyl ammonium resorcinarenes bind the larger nonspherical anions into deformed cavitand-like structures and enforce a transformation of the resorcinarene conformation from almost symmetrical to extremely distorted.

Weak interactions between resorcinarenes and diquaternary alkyl ammonium cations

The interactions of resorcin[4]arenes 1 with alkyl ammonium cations bearing a 1,4-diazabicyclo[2.2.2]octane (DABCO) scaffold (32+, 42+ and 52+) were analyzed in the solid state by X-ray crystallography, in solution by 1H NMR spectroscopy, and in the gas phase by ESI-TOF mass spectrometry. The results are complemented with AM1 calculations and compared to previous reports on complexation studies of resorcinarenes with quaternary alkyl ammonium cations. The NMR titration results indicate that there are hardly any differences in the binding of the quaternary tetramethyl ammonium cation 2+ and the diquaternary N,N’-dimethyl DABCO dication 42+. The large N,N’-dibenzyl DABCO dication 52+ has two …

Solvent-free ball-milling subcomponent synthesis of metallosupramolecular complexes.

Subcomponent self-assembly from components A, B, C, D, and Fe(2+) under solvent-free conditions by self-sorting leads to the construction of three structurally different metallosupramolecular iron(II) complexes. Under carefully selected ball-milling conditions, tetranuclear [Fe4 (AD2 )6 ](4-) 22-component cage 1, dinuclear [Fe2 (BD2 )3 ](2-) 11-component helicate 2, and 5-component mononuclear [Fe(CD3 )](2+) complex 3 were prepared simultaneously in a one-pot reaction from 38 components. Through subcomponent substitution reaction by adding subcomponent B, the [Fe4 (AD2 )6 ](4-) cage converts quantitatively to the [Fe2 (BD2 )3 ](2-) helicate, which, in turn, upon addition of subcomponent C, …

Anion-controlled formation of an aminal-(bis)imine Fe(ii)-complex.

In the presence of triflate as the counter anion, 1,2-diaminobenzene and 2-formylpyridine self-sort with iron(II) to a low-spin [Fe(L1)](OTf)2 complex in which both aminal and imine moieties coexist simultaneously, while under similar conditions the chloride anion leads to a high-spin [Fe(L2)Cl2] complex.

Switchable Access to Different Spirocyclopentane Oxindoles by N-Heterocyclic Carbene Catalyzed Reactions of Isatin-Derived Enals and N-Sulfonyl Ketimines

A novel NHC-catalyzed annulation protocol for the asymmetric synthesis of biologically important β-lactam fused spirocyclopentane oxindoles with four contiguous stereocenters, including two quaternary carbon centers, was developed. Alternatively, spirocyclopentane oxindoles containing an enaminone moiety can be achieved using the same starting materials, isatin-derived enals, and N-sulfonyl ketimines, in the presence of a slightly different NHC catalytic system. This switchable annulation strategy enables the selective assembly of both heterocyclic scaffolds with good yields and excellent enantioselectivities for a broad range of substrates.

Asymmetric, Three-Component, One-Pot Synthesis of Spiropyrazolones and 2,5-Chromenediones from Aldol Condensation/NHC-Catalyzed Annulation Reactions

A novel one-pot, three-component diastereo- and enantioselective synthesis of spiropyrazolones has been developed involving the aldol condensation of an enal to generate α,β-unsaturated pyrazolones, which react with a second equivalent of enal through an N-heterocyclic carbene (NHC)-catalyzed [3+2] annulation. The desired spirocyclopentane pyrazolones are obtained in moderate to good yields and good to excellent stereoselectivities. Alternatively, starting from cyclic 1,3-diketones, 2,5-chromenediones are available through [2+4] annulation.

Bringing a Molecular Plus One: Synergistic Binding Creates Guest-Mediated Three-Component Complexes

Cethyl-2-methylresorcinarene (A), pyridine (B), and a set of 10 carboxylic acids (Cn) associate to form A·B·Cn ternary assemblies with 1:1:1 stoichiometry, representing a useful class of ternary systems where the guest mediates complex formation between the host and a third component. Although individually weak in solution, the combined strength of the multiple noncovalent interactions organizes the complexes even in a highly hydrogen-bond competing methanol solution, as explored by both experimental and computational methods. The interactions between A·B and Cn are dependent on the pKa values of carboxylic acids. The weak interactions between A and C further reinforce the interactions betw…

Ein enantiomerenreines metallosupramolekulares Pd4L8-Aggregat mit neuartigem Strukturmotiv: Bildung durch einen Anionen-Templateffekt

Ein enantiomerenreiner Bis(3-pyridyl)-Ligand 1 auf der Basis eines BINOL-Gerusts bildet mit tetravalenten PdII-Ionen einen homochiralen [Pd4(1)8]-Komplex. Zwei Tetrafluoroborationen dienen dabei als Template fur die Bildung dieses Aggegates und werden in zwei periphere Kavitaten eingeschlossen. Die dadurch resultierende Struktur reprasentiert ein neues Strukturmotiv fur diese Sorte von metallosupramolekularen Assemblaten, in dem die vier Palladiumionen in einer verzerrt tetraedrischen Anordnung zu finden sind. Dies zwingt den Liganden 1, zwei verschiedene Konformationen in dem Aggregat einzunehmen. Beide Phanomene sind einzigartig und fuhren uberdies zur Bildung einer dreidimensionalen Stru…

Mechanochemical Synthesis, Photophysical Properties, and X-ray Structures of N-Heteroacenes (Eur. J. Org. Chem. 7/2016)

Short X···N Halogen Bonds With Hexamethylenetetraamine as the Acceptor

Hexamethylenetetramine (HMTA) and N-haloimides form two types of short (imide)X···N and X–X···N (X = Br, I) halogen bonds. Nucleophilic substitution or ligand-exchange reaction on the peripheral X of X–X···N with the chloride of N-chlorosuccinimide lead to Cl–X···N halogen-bonded complexes. The 1:1 complexation of HMTA and ICl manifests the shortest I···N halogen bond [2.272(5) Å] yet reported for an HMTA acceptor. Two halogen-bonded organic frameworks are prepared using 1:4 molar ratio of HMTA and N-bromosuccinimide, each with a distinct channel shape, one possessing oval and the other square grid. The variations in channel shapes are due to tridentate and tetradentate (imide)Br···N coordi…

Gold(I)-doped films: new routes for efficient room temperature phosphorescent materials

The synthesis of four novel gold(I)-phosphane complexes coordinated to 9-phenanthrene chromophore has been carried out through the reaction of 9-phenanthreneboronic acid and the corresponding AuClPR3 (PR3 = PPh3 for triphenylphosphane (1a); 1,4-bis(diphenylphosphanyl)butane or dppb (2b); bis(diphenylphosphanyl)acetylene or dppa (2c); (AuCl)2(diphos) (diphos = bis(diphenylphosphanyl)methane or dppm (3)) sources. The X-ray crystal structures of compounds 1a and 2b show the existence of MOF-like intermolecular assemblies that contain empty inner cavities in the absence of aurophilic contacts. In contrast, the formation of a tetranuclear complex with intramolecular aurophilic interactions was e…

Chiral hemicucurbit[8]uril as an anion receptor: selectivity to size, shape and charge distribution† †Electronic supplementary information (ESI) available: MS, NMR, dynamic NMR and computational details and a DFT-based video of complexation. CCDC 1514736–1514741, 1521388. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6sc05058a Click here for additional data file. Click here for additional data file. Click here for additional data file.

Chiral (all-R)-cyclohexanohemicucurbit[8]uril binds anions in a 1 : 1 ratio in pure methanol like a molecular Pac-Man™ with remarkable selectivity based on the size, shape and charge distribution of the anion.

ChemInform Abstract: Dimeric Resorcin[4]arene Capsules in the Solid State

Supramolecular chemistry research is focused on the study of weak non-covalent intermolecular — that is, supramolecular — interactions as the driving force in self-assembly and molecular recognition. Dimeric resorcin[4]arenes capsules have been a focus of our research for the last 15 years. This review describes the solid state complexation studies of unsubstituted phenolic resorcin[4]arenes and pyrogall[4]arenes towards the formation of dimeric capsules and assemblies using ionic and neutral species as guest molecules and templates. The multitude of different crystal structures obtained during these studies demonstrates the versatile nature of resorcin[4]arenes and pyrogall[4]arenes (2-hyd…

Anion-π Interaction: An Influential Force in Solid State Molecular Microstructures

The crystal structures of simple triphenyl(pentafluorobenzyl)phosphonium salts provide crucial data on the influence of anion size on the molecular structure of bis(pentafluorobenzyl)phosphonium cations containing two adjacent electron-deficient moieties. Whereas the bromide anions interact by anion-π interaction in a 1:1 mode with the pentafluorobenzene unit Z-configured, the bulkier anions iodide, tetrafluoroborate, and hexafluorophosphate result in a 1:2 tweezer-like anti-configuration in which one anion interacts simultaneously with two pentafluorobenzene units. When spatial separation of the two electron-deficient rings match the size of the anion, anion-π interactions induce a conform…

Pot-Economy Autooxidative Condensation of 2-Aryl-2-lithio-1,3-dithianes

The autoxidative condensation of 2-aryl-2-lithio-1,3-dithianes is here reported. Treatment of 2-aryl-1,3-dithianes with n-BuLi in the absence of any electrophile leads to condensation of three molecules of 1,3-dithianes and formation of highly functionalized α-thioether ketones orthothioesters in 51-89% yields upon air exposure. The method was further expanded to benzaldehyde dithioacetals, affording corresponding orthothioesters and α-thioether ketones in 48-97% yields. The experimental results combined with density functional theory studies support a mechanism triggered by the autoxidation of 2-aryl-2-lithio-1,3-dithianes to yield a highly reactive thioester that undergoes condensation wi…

N‐Heterocyclic Carbene Catalyzed [4+2] Annulation of Enals via a Double Vinylogous Michael Addition: Asymmetric Synthesis of 3,5‐Diaryl Cyclohexenones

A strategy for the N-heterocyclic carbene (NHC) catalyzed asymmetric synthesis of 3,5-diaryl substituted cyclohexenones has been developed via oxidative [4+2] annulation of enals and alkenylisoxazoles. It is the first example of using NHC organocatalysis in a double vinylogous Michael type reaction, a challenging but highly desirable topic. This unprecedented protocol affords good yields as well as high to excellent diastereo- and enantioselectivities.

Palladium Catalyzed [3+2] Cycloaddition of Vinyl Aziridine and Indane-1,3-diones: Diastereo- and Enantioselective Access to Spiro-Pyrrolidines

A mild and efficient palladium-catalyzed [3+2] cycloaddition of vinylaziridine and indane-1,3-diones has been realized. The resulting spiro-pyrrolidines were provided in excellent yields and, with the introduction of the leucine-derived phosphine ligand, moderate to good enantio­- and diastereoselectivities.

Tetrameric and Dimeric [N∙∙∙I+∙∙∙N] Halogen-Bonded Supramolecular Cages

Tripodal N‐donor ligands are used to form halogen‐bonded assemblies via structurally analogous Ag+‐complexes. Selective formation of discrete tetrameric I6L4 and dimeric I3L2 halonium cages, wherein multiple [N⋅⋅⋅I+⋅⋅⋅N] halogen bonds are used in concert, can be achieved by using sterically rigidified cationic tris(1‐methyl‐1‐azonia‐4‐azabicyclo[2.2.2]octane)‐mesitylene ligand, L1(PF6)3, and flexible ligand 1,3,5‐tris(imidazole‐1‐ylmethyl)‐2,4,6‐trimethylbenzene, L2, respectively. The iodonium cages, I6L14(PF6)18 and I3L22(PF6)3, were obtained through the [N⋅⋅⋅Ag+⋅⋅⋅N]→ [N⋅⋅⋅I+⋅⋅⋅N] cation exchange reaction between the corresponding Ag6L14(PF6)18 and Ag3L22(PF6)3 coordination cages, prepare…

An enantioselective synthesis of the C(33)–C(37) fragment of Amphotericin B

An enantioselective synthesis of the C(33)–C(37) tripropionate fragment of Amphotericin B has been developed in only 6 steps. Peer reviewed

Luminescent PtII and PtIV Platinacycles with Anticancer Activity Against Multiplatinum‐Resistant Metastatic CRC and CRPC Cell Models

Abstract: Platinum‐based chemotherapy persists to be the only effective therapeutic option against a wide variety of tumours. Nevertheless, the acquisition of platinum resistance is utterly common, ultimately cornering conventional platinum drugs to only palliative in many patients. Thus, encountering alternatives that are both effective and non‐cross‐resistant is urgent. In this work, we report the synthesis, reduction studies and luminescent properties of a series of cyclometallated (C,N,N’) PtIV compounds derived from amine‐imine ligands, and their remarkable efficacy at the high nanomolar range and complete lack of cross‐resistance, as an intrinsic property of the platinacycle, against …

2-Sulfoximidoyl Acetic Acids from Multicomponent Petasis Reactions and Their Use as Building Blocks in Syntheses of Sulfoximine Benzodiazepine Analogues.

Upon application of a multicomponent Petasis reaction, a broad range of NH-sulfoximines and boronic acids react with glyoxalic acid to afford the corresponding 2-substituted acetic acids with N-bound sulfoximidoyl groups. The protocol features excellent yields under ambient, metal-free conditions and short reaction times. Furthermore, the applicability of 2-sulfoximidoyl acetic acids as building blocks for synthesizing sulfoximine-based benzodiazepine analogues was demonstrated.

Observation of novel oxygen⋯oxygen interaction in supramolecular assembly of cobalt(III) Schiff base complexes: a combined experimental and computational study

Two mononuclear cobalt(III) Schiff base complexes with azide [Co(L)(N3)(L0 )] (1) and [Co(L)(N3)(L00)] (2) {where HL ¼ 1-((2-(diethylamino)ethylimino)methyl)naphthalene-2-ol, HL0 ¼ 2-hydroxy-1-naphthaldehyde and HL00 ¼ acetylacetone} have been synthesized and characterized by elemental analysis, IR and UV-Vis spectroscopy and single crystal X-ray diffraction studies. Both complexes show mononuclear structures with azide as terminal coligand. Structural features have been examined in detail that reveal the formation of interesting supramolecular networks generated through non-covalent forces including hydrogen bonding, C–H/H–C and C–H/p interactions. These interactions have been studied ener…

Synthesis of a tetradentate piperazine ligand and a structural study of its coordination compounds

Abstract A tetradentate ligand N,N′-bis(2-pyridylmethyl)piperazine (L1) and seven structures of its transition metal coordination compounds are described. Most of the compounds are of the general formula [M(L1)(NO3)2], with M=Cu2+, Co2+, Mn2+and Cd2+. In addition, a dimeric copper(II) compound, [Cu2(L1)(Ac)4](H2O)3, and polymeric silver(I) compounds, [Ag(L1)]n(NO3)n(EtOH)n and [Ag(L1)]n(SO3CF3)n, were formed. The overall structure of L1 in the metal complexes A–G varies with the size and electronic properties of the metal ions. Mononuclear complex A is a five-coordinated, B is a six-coordinated, and C and D are eight-coordinated metal complexes. The dinuclear Cu complex, E, is four-coordina…

Crystal structure of a CsF-uranyl-salen complex. An unusual cesium-chlorine coordination.

Complexation of CsF with the ditopic uranyl-salen receptor results in a solid-state structure, in which the coordination sphere of cesium is filled by ligation to one of the chlorine atoms of the solvent chloroform. This X-ray structure is the first example of chloroform ligation to an alkali-metal ion.

Novel one-pot synthesis of quaternary ammonium halides: new route to ionic liquids

Treatment of an amide with an alkyl or substituted alkyl halide in the presence of a weak base in a one-pot reaction leads to crystalline quaternary ammonium halides with reasonable chemical yields; some of the compounds show low melting points and a liquid range of over 50–100 °C before decomposition.

Accelerated dinuclear palladium catalyst identification through unsupervised machine learning.

Although machine learning bears enormous potential to accelerate developments in homogeneous catalysis, the frequent need for extensive experimental data can be a bottleneck for implementation. Here, we report an unsupervised machine learning workflow that uses only five experimental data points. It makes use of generalized parameter databases that are complemented with problem-specific in silico data acquisition and clustering. We showcase the power of this strategy for the challenging problem of speciation of palladium (Pd) catalysts, for which a mechanistic rationale is currently lacking. From a total space of 348 ligands, the algorithm predicted, and we experimentally verified, a number…

Asymmetric Synthesis of Amino-Bis-Pyrazolone Derivatives via an Organocatalytic Mannich Reaction.

A new series of N-Boc ketimines derived from pyrazolin-5-ones have been used as electrophiles in asymmetric Mannich reactions with pyrazolones. The amino-bis-pyrazolone products are obtained in excellent yields and stereoselectivities by employing a very low loading of 1 mol % of a bifunctional squaramide organocatalyst. Depending on the substitution at position 4 of the pyrazolones, the new protocol allows for the generation of one or two tetrasubstituted stereocenters, including a one-pot version combing the Mannich reaction with a base-mediated halogenation. peerReviewed

Solution stoichiometry determines crystal stoichiometry in halogen-bonded supramolecular complexes

The behavior of the methylisonicotinate (MINC) building block as halogen bonding-acceptor module has been investigated in the solid state. Both the N and the O atoms of MINC interact with the iodine atoms of 1,4-diiodotetrafluorobenzene (DITFB) giving rise to N⋯I and O⋯I interactions. Hierarchy between these interactions allows the control of the composition and thus the structure of the supramolecular complex, according to the composition of the reaction mixture. A structure based on an infinite chain and a trimeric supermolecule have been obtained starting from a 1 ∶ 1 MINC/DITFB stoichiometry or by using a large excess of MINC, respectively. While the former structure shows simultaneous …

Counterion influence on the N–I–N halogen bond† †Electronic supplementary information (ESI) available: Experimental details of synthesis, compound characterisation, IPE NMR measurements, computational and crystallographic procedures, and crystal data for 1-Ag/I to 7-Ag/I, and 12-Ag. CCDC 1045981–1045995. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01053e Click here for additional data file. Click here for additional data file.

Counterions influence three-center halogen bonds differently than coordination bonds of transition metals.

Role of Weak Hydrogen Bonds and Halogen Bonds in 5-Halo-1,3-dimethyluracils and Their Cocrystals—A Combined Experimental and Computational Study

Seven single crystals containing either N,N-dimethyluracil (DMHU) or one of its 5-halogenated derivatives (DMXU; X = F, Cl, Br, I) were prepared using N,N-dimethylformamide as the crystallization solvent. Single crystal X-ray diffraction and quantum chemical calculations carried out at the spin component scaled local MP2 level of theory were then used to study the intramolecular halogen and nonconventional hydrogen bonds present in the structures. The results were compared to and contrasted with the previously reported data for uracil and its halogenated derivatives. In particular, the intermolecular interactions in DMIU were compared to the halogen and hydrogen bonds in 5-iodouracil that, …

Iodine(I) and Silver(I) Complexes of Benzoimidazole and Pyridylcarbazole Derivatives

The synthesis of iodine(I) complexes with either benzoimidazole or carbazole-derived sp 2 N -containing Lewis bases is described, as well as their corresponding silver(I) complexes. The addition of elemental iodine to the linear two-coordinate Ag(I) complexes produces iodine(I) complexes with a three-center four-electron (3c-4e) [N — I — N] + bond. The 1 H and 1 H- 15 N HMBC NMR studies unambiguously confirm the formation of the complexes in all cases via the [N — Ag — N] + → [N — I — N] + cation exchange, with the 15 N NMR chemical shift change between 94 to 111 ppm when compared to the free ligand. The single crystal X-ray crystallographic studies on four I + complexes revealed highly sym…

Metal-Organic Nanocapsules with Functionalized s-Heptazine Ligands.

A metalloorganic capsule was synthesized where the ligand is a derivative of heptazine with three carboxylic groups that are coordinated to CuII cations, forming paddle-wheel motifs. Each nanocapsule is neutral, with 12 CuII centers and 8 ligands adopting a rhombicuboctahedron shape. It has almost 3 nm diameter, and the main intermolecular interactions in the solid are π··· π stacking between the C6N7 heptazine moieties. The nanocapsules can form monolayers deposited on graphite as observed by atomic force microscopy, which confirms their stability in solution. peerReviewed

Multifacial Recognition in Binary and Ternary Cocrystals from 5-Halouracil and Aminoazine Derivatives

A systematic analysis using single crystal X-ray diffraction was performed to explore the role exerted by potential intercomponent proton-transfer reactions in the supramolecular structures of A–B cocrystals formed by 5-haloderivatives of uracil (A), coupled with 2-aminoadenine simulants (aminoazines, B). Twelve new heterodimers were synthesized in different stoichiometries and cocrystallized by solvent cogrinding followed by solution crystallization. In the binary cocrystals, uracil or 1-methyluracil with halide modification at the 5 position (F, Cl, Br, I) was coupled with amino-aromatic N-heterocycles (melamine, 2,4,6-triaminopyrimidine, 2,6-diaminopyridine) as a multivalent site for pyr…

Geometrically diverse anions in anion–π interactions

The role of different anion geometries in anion–π interactions is discussed. The chemistry described herein is different to the interaction of spherical cations with aromatics. The influence of different geometries makes selective anion recognition more complicated than respective cation sensing. The present structural study reveals attractive interactions between pentafluorophenyl units and geometrically diverse anions (linear, trigonal planar, tetrahedral and octahedral). Due to the electrostatic nature of anion–π interactions, the anion geometry seems to be irrelevant. The size of the anion controls the relative orientation of the anion and the π system (e.g. in compounds 1–3). The dimer…

N-Glycosylamines of 4,6-O-ethylidene-alpha-D-glucopyranose: synthesis, characterisation and structure of CO2H, Cl and F ortho-substituted phenyl derivatives and metal ion complexes of the CO2H derivative

A saccharide based ligand suitable for metal binding (HLCOOH) has been synthesized using 4,6-O-ethylidene-alpha-D-glucopyranose (4,6-O-EGP) and anthranilic acid. A few analogous glycosylamines with chloro and fluoro ortho substitutions have also been synthesized and characterised. Complexes of HLCOOH with Na+, K+, Mg2+, Ca2+, Ba2+, Cd2+ and Hg2+ have been isolated and characterised fully. The crystal structures of 4,6-O-EGP, the chloro analogue of HLCOOH and the K+ complex of L-COOH are established. The anomeric nature, orientation of the binding core and the co-ordination aspects of K+ have been derived from these structures.

Iodine(I) and Silver(I) Complexes Incorporating 3-Substituted Pyridines

Building upon the first report of a 3-acetaminopyridine-based iodine(I) complex (1b) and its unexpected reactivity toward tBuOMe, several new 3-substituted iodine(I) complexes (2b–5b) have been synthesized. The iodine(I) complexes were synthesized from their analogous silver(I) complexes (2a–5a) via a silver(I) to iodine(I) cation exchange reaction, incorporating functionally related substituents as 3-acetaminopyridine in 1b; 3-acetylpyridine (3-Acpy; 2), 3-aminopyridine (3-NH2py; 3), and 3-dimethylaminopyridine (3-NMe2py; 4), as well as the strongly electron-withdrawing 3-cyanopyridine (3-CNpy; 5), to probe the possible limitations of iodine(I) complex formation. The individual properties …

Modulation of N···I and +N−H···Cl−···I Halogen Bonding: Folding, Inclusion, and Self-Assembly of Tri- and Tetraamino Piperazine Cyclophanes

The acidity of the crystallization conditions was successfully employed in modulating the balance between the robust intramolecular hydrogen bonding (HB) and intermolecular halogen bonding (XB) observed in large tri- (1) and tetraamino (2) piperazine cyclophanes. A careful crystallization of the title XB acceptor cyclophanes with a strong bidentate XB donor 1,4-diiodotetrafluorobenzene (F4DIB) from CHCl3:MeOH, dimethylformamide (DMF), or HCl:H2O:EtOH resulted in X-ray quality crystals of 1·F4DIB, 2@DMF, 2·2@F4DIB, [1H3]Cl3·(F4DIB)6, and [2H6]Cl6·(F4DIB)2. The intramolecular hydrogen bonding pattern in 1 and 2 was retained in neutral protic and aprotic solvents, and regular N−H···N hydrogen …

The subtle balance of weak supramolecular interactions: The hierarchy of halogen and hydrogen bonds in haloanilinium and halopyridinium salts

The series of haloanilinium and halopyridinium salts: 4-IPhNH3Cl (1), 4-IPhNH3Br (5), 4-IPhNH3H2PO4 (6), 4-ClPhNH3H2PO4 (8), 3-IPyBnCl (9), 3-IPyHCl (10) and 3-IPyH-5NIPA (3-iodopyridinium 5-nitroisophthalate, 13), where hydrogen or/and halogen bonding represents the most relevant non-covalent interactions, has been prepared and characterized by single crystal X-ray diffraction. This series was further complemented by extracting some relevant crystal structures: 4-BrPhNH3Cl (2, CCDC ref. code TAWRAL), 4-ClPhNH3Cl (3, CURGOL), 4-FPhNH3Cl (4, ANLCLA), 4-BrPhNH3H2PO4, (7, UGISEI), 3-BrPyHCl, (11, CIHBAX) and 3-ClPyHCl, (12, VOQMUJ) from Cambridge Structural Database for sake of comparison. Bas…

A convenient route for the preparation of the monohydride catalyst trans-[RuCl(H)(dppe)2] (dppe=Ph2PCH2CH2PPh2): improved synthesis and crystal structure

Abstract A novel and improved room temperature synthesis of the monohydride catalyst trans-[RuCl(H)(dppe)2] complex (1, dppe (1,2-bis(diphenylphosphino)ethane) = Ph2PCH2CH2PPh2) proceeds through oxidation of methanol (the solvent) by the pentacoordinated cis-[RuCl(dppe)2][PF6] complex and t-BuOK as the base is described. Compound 1 was fully characterized by NMR (1H, 13C, 31P), ESI-MS(TOF +), FTIR and elemental analysis. The X-ray structure of 1 was reported for the first time and unambiguously confirms the trans-configuration of the complex.

Synthesis and characterization of chiral azobenzene dye functionalized Janus dendrimers

Abstract Eight bischromophoric bisMPA based polyester Janus dendrimers emanating from a pentaerythritol core were synthesized and their properties evaluated. 4-((4-(Ethyl(2-(2-(6-methoxynaphthalen-2-yl)propanoyloxy)ethyl)amino)-phenyl)diazenyl)-benzoic acid and 4-((4-(ethyl(2-(2-(6-methoxynaphthalen-2-yl)propanoyloxy)-ethyl)-amino)phenyl)diazenyl)-3-nitrobenzoic acid were attached to the dendritic polyester skeleton to make chiral dendrimers up to the second generation. The structures and the purity of the molecules were verified with 1H NMR, 13C NMR, ESI TOF mass spectrometry, and elemental analysis. Spectral properties were evaluated with UV–vis and CD spectrometer. The compounds displaye…

Tetranitroresorcin[4]arene: synthesis and structure of a new stereoisomer

The direct reaction between 2-nitroresorcinol and acetaldehyde in alkaline medium yields tetranitro-C1-resorcin[4]arene in a moderate 8.2% overall yield which was characterized by single crystal X-ray crystallography, 1H NMR spectroscopy and electrospray ionization mass spectrometry (ESI-MS). In solution and in the solid state, the product adopts a unique, thermally stable and unprecedented rcct-boat conformation.

Strontium complexes of calixarene amides in the solid state: structural dependence on the ligand size and on the counter ions

For the first time, crystal structures of three strontium complexes of calixarene amides have been determined. A p-tert-butylcalix[6]arene hexaamide forms a 1∶1 complex with Sr(Pic)2 (Pic = picrate), whereas p-tert-butylcalix[8]arene and p-methoxycalix[8]arene octaamides encapsulate two strontium cations each. The binding geometries of the metal cations depend on the ligand size and on the counter anion used (chloride or picrate).

N-[1-(Silatran-1-yl)propyl]pentafluorobenzamide

In the title compound {systematic name: N-[3-(5-aza-2,8,9-trioxa-1-silabicyclo­[3.3.3]undeca­n-1-yl)propyl]penta­fluorobenzamide}, C16H19F5N2O4Si, unexpected weak anion⋯π-type C=O⋯C(aromatic) inter­actions form a dimer [O⋯C distances of 3.096 (3) and 3.036 (3) A]. These dimers are further connected by a normal N—H⋯O hydrogen bond [2.955 (2) A], from the amide H atom to one of the silatrane O atoms. Also, four intermolecular contacts between CH groups and silatrane O and F atoms [3.101(3)–3.406 (3) A] are observed.

Nanomolar pyrophosphate detection in water and in a self-assembled hydrogel of a simple terpyridine-Zn2+ complex.

A simple terpyridine-Zn(II) complex is shown to act as an efficient and highly selective fluorescent sensor for pyrophosphate in water at physiological pH. The sensor complex showed an unprecedented fluorescence response (∼500 fold increase) and a record nanomolar sensitivity (detectable fluorescent response at 20 nM and LOD ∼ 0.8 nM). It has successfully been used to stain and record confocal fluorescence microscopy images of HeLa cells. Moreover, the complex was found to self-assemble into a hydrogel which was subsequently used to coat disposable paper strips for easy, low-cost detection of pyrophosphate.

A Simple Organocatalytic Enantioselective Synthesis of Pregabalin

This paper describes a new procedure for the enantioselective synthesis of the important anticonvulsant drug Pregabalin, which shows biological properties as the (S) enantiomer only. The key step of the synthetic sequence is the Michael addition reaction of Meldrum's acid to a nitroalkene mediated by a quinidine derived thiourea. A variety of novel catalysts bearing different groups at the thiourea moiety were synthesized and tested. The most successful catalyst that incorporates a trityl substituent provided up to 75 % ee of (S)-4. The conjugate addition reaction was carried out on a multigram scale with low loadings of catalyst (10 mol-%). Moreover, the catalyst can be recycled showing th…

Dihypoiodites stabilised by 4-ethylpyridine through O–I–N halogen bonds

Four bis(O–I–N) compounds have been synthesised from various dihypoiodites and 4-ethylpyridine. The compounds were characterised in both the solution and solid states by NMR spectroscopy (1H, 15N), X-ray diffraction, and computational calculations. peerReviewed

Chiral Self-Sorting of trans-Chelating Chiral Ligands upon Formation of PdII Complexes

Invited for the cover of this issue is the group of Arne Lutzen at the University of Bonn, Germany. The cover image shows two dissymmetric bis(3-pyridyl) ligands based on a planar chiral pseudo-ortho-disubstituted [2.2]paracyclophane scaffold. Upon forming a mononuclear [ML2] complex with palladium(II) ions, these ligands act in a trans-chelating manner and undergo complete chiral self-sorting.

[3+2]‐Cycloadditions of N ‐Cyano Sulfoximines with 1,3‐Dipoles

Involving the cyano group of N‐cyano sulfoximines in [3+2]‐cycloaddition reactions with 1,3‐dipoles provides practical routes for the construction of 5‐membered heterocycles bearing sulfoximinoyl moieties. An ytterbium‐catalyzed cycloaddition utilizing hydrazonoyl chlorides was developed, as well as a reaction involving imidoyl chlorides proceeding without the aid of a catalyst. Following these protocols, a range of sulfoximines with N‐1,2,4‐triazolyl and N‐1,2,4‐oxadiazolyl substituents was prepared. peerReviewed

Stepwise Construction of Heterobimetallic Cages by an Extended Molecular Library Approach.

Two novel heterobimetallic complexes, a trigonal-bipyramidal and a cubic one, have been synthesized and characterized using the same C3-symmetric metalloligand, prepared by a simple subcomponent self-assembly strategy. Adopting the molecular library approach, we chose a mononuclear, preorganized iron(II) complex as the metalloligand capable of self-assembly into a trigonal-bipyramidal or a cubic aggregate upon coordination to cis-protected C2-symmetric palladium(II) or unprotected tetravalent palladium(II) ions, respectively. The trigonal-bipyramidal complex was characterized by NMR and UV–vis spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffrac…

A self-assembled M8L6 cubic cage that selectively encapsulates large aromatic guests.

Porphyrins cubed: A series of self-assembled M8L6 cubic cages that enclose a volume in excess of 1300 A3 were synthesized (see scheme). The porphyrinic walls of the cubes provide favorable sites for pnp interactions, leading to selectivity between large and chemically similar aromatic guests: three molecules of coronene are incorporated and the higher fullerenes C70nC84 are selectively bound in the presence of

Dihalogens as Halogen Bond Donors

Asymmetric Organocatalytic Michael Addition–Cyclization Cascade of Cyclopentane-1,2-dione with Substituted α,β-Unsaturated Aldehydes

An asymmetric organocatalytic Michael addition–cyclization cascade reaction has been developed using cyclopentane-1,2-dione as a Michael donor and α,β-unsaturated aldehydes as Michael acceptors. Bicyclic hemiacetals were obtained in excellent yields and enantioselectivities. On the basis of the results, a one-pot reaction has been developed to obtain chiral 3-substituted cyclopentane-1,2-diones and substituted dihydropyrans in good yields and excellent enantioselectivity.

Strategies for Exploring Functions from Dynamic Combinatorial Libraries

Dynamic combinatorial chemistry (DCC) is a powerful approach for creating complex chemical systems, giving access to the studies of complexity and exploration of functionality in synthetic systems. However, compared with more advanced living systems, the man‐made chemical systems are still less functional, due to their limited complexity and insufficient kinetic control. Here we start by introducing strategies to enrich the complexity of dynamic combinatorial libraries (DCLs) for exploiting unexpected functions by increasing the species of building blocks and/or templates used. Then, we discuss how dynamic isomerization of photo‐switchable molecules help DCLs increase and alter the systemic…

Crystal structures and thermal behavior of bis[dibenzyldimethylammonium]CuBr4, bis[dibenzyldimethylammonium]CuCl4 and bis[dimethyldi(2-phenylethyl)ammonium]CuBr4 crystallized from acetonitrile and dilute HX (X=Cl or Br) solutions

Abstract Bis[dibenzyldimethylammonium]CuBr4, bis[dibenzyldimethylammonium]CuCl4 and bis[dimethyldi(2-phenylethyl)ammonium]CuBr4 were crystallized from acetonitrile and/or dilute HX solutions. Five different kinds of single crystals were obtained. In the case of bis[dibenzyldimethylammonium]CuX4 (X=Br or Cl), the acetonitrile molecules cocrystallized into the crystal structure when acetonitrile solution was used. As a result, the isomorphic structures of Bis[dibenzyldimethylammonium]CuX4·0.5 CH3CN (X=Br or Cl) in monoclinic space group P21/n were obtained. When a dilute HX solution was used, the bis[dibenzyldimethylammonium]CuX4 (X=Br or Cl) crystallized without solvent molecules. The formed…

Strong Emission Enhancement in pH‐Responsive 2:2 Cucurbit[8]uril Complexes

Organic fluorophores, particularly stimuli-responsive molecules, are very interesting for biological and material sciences applications, but frequently limited by aggregation- and rotation-caused photoluminescence quenching. A series of easily accessible bipyridinium fluorophores, whose emission is quenched by a twisted intramolecular charge-transfer (TICT) mechanism, is reported. Encapsulation in a cucurbit[7]uril host gave a 1:1 complex exhibiting a moderate emission increase due to destabilization of the TICT state inside the apolar cucurbituril cavity. A much stronger fluorescence enhancement is observed in 2:2 complexes with the larger cucurbit[8]uril, which is caused by additional con…

Halogen bonding and host–guest chemistry between N-alkylammonium resorcinarene halides, diiodoperfluorobutane and neutral guests

Single crystal X-ray structures of halogen-bonded assemblies formed between host N-hexylammonium resorcinarene bromide (1) or N-cyclohexylammonium resorcinarene chloride (2), and 1,4-diiodooctafluorobutane and accompanying small solvent guests (methanol, acetonitrile and water) are presented. The guests’ inclusion affects the geometry of the cavity of the receptors 1 and 2, while the divalent halogen bond donor 1,4-diiodooctafluorobutane determines the overall nature of the halogen bond assembly. The crystal lattice of 1 contains two structurally different dimeric assemblies A and B, formally resulting in the mixture of a capsular dimer and a dimeric pseudo-capsule. 1H and 19F NMR analyses …

Bis-urea macrocycles with a deep cavity.

Two configurational isomers of bis-urea macrocycles have been synthesized, and their neutral molecule recognition was studied by X-ray crystallography and (1)H NMR experiments. Cooperative action between the deep cavity and the urea groups and the influence of dipole alignments on molecular recognition are discussed.

Asymmetric [N–I–N]+ halonium complexes

The first asymmetric halogen-bonded iodonium complexes [I(py)(4-DMAP)]PF6 (2c) and [I(py)(4-Etpy)]PF6 (2e) were prepared via [N-Ag-N]+ → [N-I-N]+ cation exchange of their analogous 2-coordinate silver complexes. The complexes were characterised by 1H and 1H-15N HMBC NMR spectroscopy, and single crystal X-ray crystallography. peerReviewed

Formation of Triple‐Stranded Dinuclear Helicates with Dicatecholimine Ligands: The Influence of Steric Hindrance at the Spacer

A series of new imine-bridged dicatechol ligands 3a–f-H4 with sterically demanding groups at the spacers are used for the formation of titanium(IV) complexes M4[(3)3Ti2]. All three ligands 3a–c-H4 form triple-stranded dinuclear helicates. When the bulky ligands 3a-H4 or 3c-H4 are used with potassium as the countercation, oligomeric or polymeric side products are also observed. The imine-bridged ligand 3e-H4 quantitatively forms helicates M4[(3e)3Ti2] and not a M4L6 tetrahedron as observed with Raymond’s analogous amide-bridged dicatechol ligand 3i-H4. NMR spectroscopic investigations at variable temperature show that ligand 3f-H4, which possesses a spiro fluorenyl group at the central unit …

Resorcinarene-based ATRP initiators for star polymers

Two novel multifunctional initiators for atom transfer radical polymeriza- tion (ATRP) were synthesized by derivatization of tetraethylresorcinarene. The deri- vatization induced a change in the conformation of the resorcinarene ring, which was confirmed by NMR spectroscopy. The initiators were used in ATRP of tert-butyl acrylate and methyl methacrylate, producing star polymers with controlled molar masses and low polydispersities. Instead of the expected star polymers with eight arms, polymers with four arms were obtained. Conformational studies on the initiators by rotating- frame nuclear Overhauser and exchange spectroscopy NMR and molecular modeling suggested that of eight initiator fun…

Simultaneous endo and exo  Complex Formation of Pyridine[4]arene Dimers with Neutral and Anionic Guests

The formation of complexes between hexafluorophosphate (PF6- ) and tetraisobutyloctahydroxypyridine[4]arene has been thoroughly studied in the gas phase (ESI-QTOF-MS, IM-MS, DFT calculations), in the solid state (X-ray crystallography), and in chloroform solution (1 H, 19 F, and DOSY NMR spectroscopy). In all states of matter, simultaneous endo complexation of solvent molecules and exo complexation of a PF6- anion within a pyridine[4]arene dimer was observed. While similar ternary complexes are often observed in the solid state, this is a unique example of such behavior in the gas phase.

Tri- and tetraurea piperazine cyclophanes: synthesis and complexation studies of preorganized and folded receptor molecules.

A series of symmetrical tri- and tetrameric N-ethyl- and N-phenylurea-functionalized cyclophanes have been prepared in nearly quantitative yields (86-99 %) from the corresponding tri- and tetraamino-functionalized piperazine cyclophanes and ethyl or phenyl isocyanates. Their conformational and complexation properties have been studied by single-crystal X-ray diffraction, variable-temperature NMR spectroscopy, and ESI-MS analysis. The rigid 27-membered trimeric cyclophane skeleton assisted by a seam of intramolecular hydrogen bonds results in a preorganized ditopic recognition site with an all-syn conformation of the urea moieties that, complemented by a lipophilic cavity of the cyclophane, …

Mass Spectrometric Investigation of Noncovalent Complexation between a Tetratosylated Resorcarene and Alkyl Ammonium Ions

Noncovalent complexation between tetratosylated tetraethyl resorcarene (1) and primary, secondary, and tertiary alkyl ammonium ions (mMe, dMe, tMe, mEt, dEt, tEt, dBu, and dHex) was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Interactions of the noncovalent complexes were investigated by means of competition experiments, collision-induced dissociation (CID) experiments, ion-molecule reactions with tripropylamine and gas phase H/D-exchange reactions with deuteroammonia. Gas phase ion-molecule reactions gave especially valuable information about the structure and properties of the complexes. Resorcarene 1 formed relatively stable…

Self-Assembly, Characterisation, and Crystal Structure of Multinuclear Metal Complexes of the [2×3] and [3×3] Grid-Type

The self-assembly of new multimetallic complexes of grid-type architecture is described. The binding of a set of tris-terdentate ligands, 1 a-1 d, based on terpyridine-like subunits, with different octahedrally coordinated metal ions leads to the formation of species whose structure depends strongly on the ligand, the metal ion, the counterion, the solvent, and the reaction conditions. Under suitable conditions, the [3 x 3] grid was obtained from the reaction of ligand 1 a with zinc tetrafluoroborate and from ligand 1 b with mercury triflate. The other ligands led to the formation of mainly one compound of composition [M(6)L(5)](12+), which has the structure of an incomplete [2 x 3] grid. T…

Encapsulation of secondary and tertiary ammonium salts by resorcinarenes and pyrogallarenes: the effect of size and charge concentration

The binding of different categories of alkyl ammonium (secondary and tertiary mono- and di-ammonium) salts with resorcinarenes and a pyrogallarene through weak interactions was analysed in all phases. 1H NMR spectroscopy and electrospray ionisation mass spectrometry were utilized in analysing the complexes in solution and in the gas phase, respectively. The 1H NMR titration studies in methanol-d4 reveal that the association constants for the 1:1 complexes vary according to the electronic properties of the hosts as well as the size, geometric orientation and charge concentration of the guest cations with binding constants of up to 950 M−1 in some cases. Mass spectrometry reveals 1:1 monomeri…

Cation-translocation based isomerism offers a tool for the expansion of compressed helicates.

A series of compressed M[Li313Ti2] (M = Li, Na, K, Rb, Cs) and expanded helicates M4[13Ti2] has been obtained. The helicates Li3[M13Ti2] or M4[13Ti2] with M = Na+, K+, Rb+, or Cs+ adopt the expanded structure in solution. By crystallization the compressed structures M[Li313Ti2] (M = Na, Rb) are obtained. This represents an example of cation-translocation based isomerism.

ChemInform Abstract: Highlights on Contemporary Recognition and Sensing of Fluoride Anion in Solution and in the Solid State

The fluoride anion has recently gained well deserved attention among the scientific community for its importance in many fields of human activities, but also for concerns on its effect on health and the environment. Although surprisingly overlooked in systematic studies in the past, fluoride has nowadays become a topical target in the field of anion recognition. A multitude of scientific reports are published every year where the establishment of efficient and specific interaction with fluoride is sought in polar and aqueous media. Here, the emphasis is directed to a detailed description of the most interesting contemporary studies in the field, with a particular focus given to those publis…

Synthesis, characterisation and crystal structures of Schiff bases from the reaction of 4,6-O-ethylidene-β-D-glucopyranosylamine with substituted salicylaldehydes

Multiple chemical modifications were carried out on D-glucose to result in the corresponding Schiff bases. Such modifications performed on D-glucose not only helped in increasing the solubility of the products in nonaqueous solvents, but also restricted the anomerisation of the saccharide moiety in solution. NMR study of the products revealed the presence of the β-anomeric form of the saccharide moiety in Me2SO solution. All the compounds were characterised by analytical and spectral methods. The literature is devoid of any crystal structures of saccharide–Schiff base combinations of the type reported in this paper. The crystal structures of these molecules exhibited a tridentate, ONO bindi…

Anion–π Interactions in Salts with Polyhalide Anions: Trapping of I 4 2−

The directionality of interaction of electron-deficient π systems with spherical anions (e.g,. halides) can be controlled by secondary effects like NH or CH hydrogen bonding. In this study a series of pentafluorophenyl-substituted salts with polyhalide anions is investigated. The compounds are obtained by aerobic oxidation of the corresponding halide upon crystallization. Solid-state structures reveal that in bromide 2, directing NH-anion interactions position the bromide ion in an η(1)-type fashion over but not in the center of the aromatic ring. The same directing forces are effective in corresponding tribromide salt 3. In the crystal, the bromide ion is paneled by four electron-deficient…

Three-Dimensional Heterocycles by 5-exo-dig Cyclizations of S-Methyl-N-ynonylsulfoximines

Upon treatment with Cs2CO3, S-methyl-N-ynonylsulfoximines undergo 5-exo-dig cyclizations to give three-dimensional heterocycles. The reactions proceed at ambient temperature with a wide range of substrates affording the corresponding products in good to excellent yields.

Titelbild: An Unlockable-Relockable Iron Cage by Subcomponent Self-Assembly (Angew. Chem. 43/2008)

A Next‐Generation Air‐Stable Palladium(I) Dimer Enables Olefin Migration and Selective C−C Coupling in Air

Abstract We report a new air‐stable PdI dimer, [Pd(μ‐I)(PCy2 tBu)]2, which triggers E‐selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. The same dimer also triggers extremely rapid C−C coupling (alkylation and arylation) at room temperature in a modular and triply selective fashion of aromatic C−Br, C−OTf/OFs, and C−Cl bonds in poly(pseudo)halogenated arenes, displaying superior activity over previous PdI dimer generations for substrates that bear substituents ortho to C−OTf.

CCDC 1912383: Experimental Crystal Structure Determination

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CCDC 2069302: Experimental Crystal Structure Determination

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CCDC 2106005: Experimental Crystal Structure Determination

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CCDC 2064863: Experimental Crystal Structure Determination

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CCDC 1051388: Experimental Crystal Structure Determination

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CCDC 2080290: Experimental Crystal Structure Determination

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CCDC 1935909: Experimental Crystal Structure Determination

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CCDC 967090: Experimental Crystal Structure Determination

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CCDC 1053244: Experimental Crystal Structure Determination

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CCDC 1450585: Experimental Crystal Structure Determination

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CCDC 1901894: Experimental Crystal Structure Determination

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CCDC 990706: Experimental Crystal Structure Determination

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CCDC 1407239: Experimental Crystal Structure Determination

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CCDC 1839830: Experimental Crystal Structure Determination

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CCDC 1952601: Experimental Crystal Structure Determination

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CCDC 1426137: Experimental Crystal Structure Determination

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CCDC 1821333: Experimental Crystal Structure Determination

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CCDC 1913149: Experimental Crystal Structure Determination

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CCDC 971033: Experimental Crystal Structure Determination

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CCDC 1481997: Experimental Crystal Structure Determination

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CCDC 2070639: Experimental Crystal Structure Determination

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CCDC 1478712: Experimental Crystal Structure Determination

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CCDC 1473236: Experimental Crystal Structure Determination

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CCDC 1551407: Experimental Crystal Structure Determination

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CCDC 2051585: Experimental Crystal Structure Determination

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CCDC 1951454: Experimental Crystal Structure Determination

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CCDC 1417789: Experimental Crystal Structure Determination

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CCDC 1950786: Experimental Crystal Structure Determination

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CCDC 1404481: Experimental Crystal Structure Determination

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CCDC 1901279: Experimental Crystal Structure Determination

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CCDC 1901884: Experimental Crystal Structure Determination

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CCDC 1959607: Experimental Crystal Structure Determination

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CCDC 967821: Experimental Crystal Structure Determination

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CCDC 2193612: Experimental Crystal Structure Determination

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CCDC 1045987: Experimental Crystal Structure Determination

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CCDC 1439190: Experimental Crystal Structure Determination

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CCDC 1450588: Experimental Crystal Structure Determination

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CCDC 915608: Experimental Crystal Structure Determination

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CCDC 913158: Experimental Crystal Structure Determination

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CCDC 1045995: Experimental Crystal Structure Determination

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CCDC 1977489: Experimental Crystal Structure Determination

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CCDC 1555956: Experimental Crystal Structure Determination

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CCDC 1910670: Experimental Crystal Structure Determination

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CCDC 901286: Experimental Crystal Structure Determination

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CCDC 1469023: Experimental Crystal Structure Determination

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CCDC 1408386: Experimental Crystal Structure Determination

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CCDC 2106359: Experimental Crystal Structure Determination

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CCDC 2000976: Experimental Crystal Structure Determination

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CCDC 1469021: Experimental Crystal Structure Determination

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CCDC 2169530: Experimental Crystal Structure Determination

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CCDC 1062272: Experimental Crystal Structure Determination

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CCDC 1935934: Experimental Crystal Structure Determination

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CCDC 1543476: Experimental Crystal Structure Determination

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CCDC 990709: Experimental Crystal Structure Determination

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CCDC 986176: Experimental Crystal Structure Determination

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CCDC 1426141: Experimental Crystal Structure Determination

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CCDC 2041029: Experimental Crystal Structure Determination

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CCDC 1577841: Experimental Crystal Structure Determination

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CCDC 1478717: Experimental Crystal Structure Determination

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CCDC 1051458: Experimental Crystal Structure Determination

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CCDC 1478716: Experimental Crystal Structure Determination

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CCDC 1935924: Experimental Crystal Structure Determination

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CCDC 1547096: Experimental Crystal Structure Determination

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CCDC 1404479: Experimental Crystal Structure Determination

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CCDC 2027290: Experimental Crystal Structure Determination

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CCDC 1938867: Experimental Crystal Structure Determination

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CCDC 216935: Experimental Crystal Structure Determination

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CCDC 1045983: Experimental Crystal Structure Determination

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CCDC 1581474: Experimental Crystal Structure Determination

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CCDC 2069303: Experimental Crystal Structure Determination

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CCDC 2068113: Experimental Crystal Structure Determination

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CCDC 993792: Experimental Crystal Structure Determination

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CCDC 997677: Experimental Crystal Structure Determination

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CCDC 2027281: Experimental Crystal Structure Determination

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CCDC 2027279: Experimental Crystal Structure Determination

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CCDC 1935922: Experimental Crystal Structure Determination

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CCDC 957915: Experimental Crystal Structure Determination

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CCDC 1953708: Experimental Crystal Structure Determination

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CCDC 1919439: Experimental Crystal Structure Determination

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CCDC 2060885: Experimental Crystal Structure Determination

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CCDC 1951280: Experimental Crystal Structure Determination

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CCDC 1938197: Experimental Crystal Structure Determination

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CCDC 1951456: Experimental Crystal Structure Determination

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CCDC 2105110: Experimental Crystal Structure Determination

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CCDC 1901885: Experimental Crystal Structure Determination

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CCDC 2000985: Experimental Crystal Structure Determination

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CCDC 1409159: Experimental Crystal Structure Determination

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CCDC 1550984: Experimental Crystal Structure Determination

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CCDC 1815761: Experimental Crystal Structure Determination

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CCDC 1005283: Experimental Crystal Structure Determination

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CCDC 1821338: Experimental Crystal Structure Determination

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CCDC 2169531: Experimental Crystal Structure Determination

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CCDC 1551402: Experimental Crystal Structure Determination

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CCDC 949721: Experimental Crystal Structure Determination

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CCDC 1966175: Experimental Crystal Structure Determination

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CCDC 1437950: Experimental Crystal Structure Determination

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CCDC 1415585: Experimental Crystal Structure Determination

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CCDC 2225069: Experimental Crystal Structure Determination

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CCDC 1525503: Experimental Crystal Structure Determination

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CCDC 967091: Experimental Crystal Structure Determination

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CCDC 1575263: Experimental Crystal Structure Determination

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CCDC 2231744: Experimental Crystal Structure Determination

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CCDC 1408378: Experimental Crystal Structure Determination

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CCDC 1557848: Experimental Crystal Structure Determination

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CCDC 1815759: Experimental Crystal Structure Determination

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CCDC 1019456: Experimental Crystal Structure Determination

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CCDC 1935930: Experimental Crystal Structure Determination

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CCDC 1437951: Experimental Crystal Structure Determination

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CCDC 1408380: Experimental Crystal Structure Determination

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CCDC 2080284: Experimental Crystal Structure Determination

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CCDC 1935936: Experimental Crystal Structure Determination

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CCDC 1497772: Experimental Crystal Structure Determination

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CCDC 955438: Experimental Crystal Structure Determination

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CCDC 1844227: Experimental Crystal Structure Determination

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CCDC 1935921: Experimental Crystal Structure Determination

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CCDC 949723: Experimental Crystal Structure Determination

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CCDC 1040204: Experimental Crystal Structure Determination

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CCDC 2242257: Experimental Crystal Structure Determination

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CCDC 1542198: Experimental Crystal Structure Determination

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CCDC 2031247: Experimental Crystal Structure Determination

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CCDC 1500638: Experimental Crystal Structure Determination

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CCDC 1951457: Experimental Crystal Structure Determination

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CCDC 1554863: Experimental Crystal Structure Determination

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CCDC 1045988: Experimental Crystal Structure Determination

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CCDC 1005269: Experimental Crystal Structure Determination

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CCDC 1550980: Experimental Crystal Structure Determination

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CCDC 2067949: Experimental Crystal Structure Determination

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CCDC 2041028: Experimental Crystal Structure Determination

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CCDC 1935927: Experimental Crystal Structure Determination

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CCDC 1519434: Experimental Crystal Structure Determination

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CCDC 1452897: Experimental Crystal Structure Determination

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CCDC 991416: Experimental Crystal Structure Determination

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CCDC 1577820: Experimental Crystal Structure Determination

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CCDC 2245212: Experimental Crystal Structure Determination

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CCDC 1938194: Experimental Crystal Structure Determination

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CCDC 2060891: Experimental Crystal Structure Determination

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CCDC 2080288: Experimental Crystal Structure Determination

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CCDC 2009942: Experimental Crystal Structure Determination

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CCDC 1556027: Experimental Crystal Structure Determination

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CCDC 1573413: Experimental Crystal Structure Determination

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CCDC 1408383: Experimental Crystal Structure Determination

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CCDC 1045990: Experimental Crystal Structure Determination

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CCDC 1935907: Experimental Crystal Structure Determination

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CCDC 969817: Experimental Crystal Structure Determination

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CCDC 1919187: Experimental Crystal Structure Determination

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CCDC 2064893: Experimental Crystal Structure Determination

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CCDC 1451726: Experimental Crystal Structure Determination

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CCDC 986175: Experimental Crystal Structure Determination

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CCDC 2068700: Experimental Crystal Structure Determination

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CCDC 1577176: Experimental Crystal Structure Determination

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CCDC 1901284: Experimental Crystal Structure Determination

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CCDC 1401637: Experimental Crystal Structure Determination

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CCDC 1846187: Experimental Crystal Structure Determination

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CCDC 1901892: Experimental Crystal Structure Determination

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CCDC 1831925: Experimental Crystal Structure Determination

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CCDC 1996938: Experimental Crystal Structure Determination

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CCDC 1453996: Experimental Crystal Structure Determination

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CCDC 1005280: Experimental Crystal Structure Determination

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CCDC 1951459: Experimental Crystal Structure Determination

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CCDC 2060888: Experimental Crystal Structure Determination

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CCDC 1061815: Experimental Crystal Structure Determination

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CCDC 2106012: Experimental Crystal Structure Determination

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CCDC 782860: Experimental Crystal Structure Determination

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CCDC 955661: Experimental Crystal Structure Determination

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CCDC 1839834: Experimental Crystal Structure Determination

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CCDC 2027299: Experimental Crystal Structure Determination

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CCDC 1478713: Experimental Crystal Structure Determination

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CCDC 1437948: Experimental Crystal Structure Determination

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CCDC 1821334: Experimental Crystal Structure Determination

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CCDC 984217: Experimental Crystal Structure Determination

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CCDC 1938193: Experimental Crystal Structure Determination

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CCDC 1818063: Experimental Crystal Structure Determination

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CCDC 2027288: Experimental Crystal Structure Determination

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CCDC 1569570: Experimental Crystal Structure Determination

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CCDC 1894864: Experimental Crystal Structure Determination

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CCDC 2041027: Experimental Crystal Structure Determination

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CCDC 1407242: Experimental Crystal Structure Determination

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CCDC 2041025: Experimental Crystal Structure Determination

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CCDC 1005278: Experimental Crystal Structure Determination

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CCDC 1426934: Experimental Crystal Structure Determination

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CCDC 977466: Experimental Crystal Structure Determination

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CCDC 936269: Experimental Crystal Structure Determination

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CCDC 1533110: Experimental Crystal Structure Determination

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CCDC 1554861: Experimental Crystal Structure Determination

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CCDC 1936526: Experimental Crystal Structure Determination

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CCDC 1478715: Experimental Crystal Structure Determination

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CCDC 1577819: Experimental Crystal Structure Determination

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CCDC 2193619: Experimental Crystal Structure Determination

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CCDC 2106008: Experimental Crystal Structure Determination

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CCDC 1406302: Experimental Crystal Structure Determination

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CCDC 1995537: Experimental Crystal Structure Determination

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CCDC 782859: Experimental Crystal Structure Determination

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CCDC 1583123: Experimental Crystal Structure Determination

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CCDC 1831622: Experimental Crystal Structure Determination

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CCDC 1014209: Experimental Crystal Structure Determination

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CCDC 936267: Experimental Crystal Structure Determination

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CCDC 1439191: Experimental Crystal Structure Determination

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CCDC 2225023: Experimental Crystal Structure Determination

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CCDC 1488064: Experimental Crystal Structure Determination

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CCDC 1818911: Experimental Crystal Structure Determination

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CCDC 1861404: Experimental Crystal Structure Determination

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CCDC 1407136: Experimental Crystal Structure Determination

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CCDC 2027300: Experimental Crystal Structure Determination

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CCDC 1429823: Experimental Crystal Structure Determination

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CCDC 1839827: Experimental Crystal Structure Determination

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CCDC 1005287: Experimental Crystal Structure Determination

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CCDC 2027289: Experimental Crystal Structure Determination

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CCDC 1014201: Experimental Crystal Structure Determination

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CCDC 1429824: Experimental Crystal Structure Determination

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CCDC 2192598: Experimental Crystal Structure Determination

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CCDC 2127765: Experimental Crystal Structure Determination

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CCDC 1992633: Experimental Crystal Structure Determination

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CCDC 1406301: Experimental Crystal Structure Determination

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CCDC 1534938: Experimental Crystal Structure Determination

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CCDC 1024471: Experimental Crystal Structure Determination

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CCDC 1516205: Experimental Crystal Structure Determination

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CCDC 915600: Experimental Crystal Structure Determination

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CCDC 1469012: Experimental Crystal Structure Determination

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CCDC 915601: Experimental Crystal Structure Determination

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CCDC 2069786: Experimental Crystal Structure Determination

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CCDC 1846185: Experimental Crystal Structure Determination

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CCDC 1443004: Experimental Crystal Structure Determination

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CCDC 2009560: Experimental Crystal Structure Determination

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CCDC 1966422: Experimental Crystal Structure Determination

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CCDC 1935919: Experimental Crystal Structure Determination

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CCDC 1839837: Experimental Crystal Structure Determination

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CCDC 1514740: Experimental Crystal Structure Determination

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CCDC 1899328: Experimental Crystal Structure Determination

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CCDC 1539540: Experimental Crystal Structure Determination

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CCDC 2080282: Experimental Crystal Structure Determination

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A conformationally adaptive macrocycle: conformational complexity and host–guest chemistry of zorb[4]arene

Large amplitude conformational change is one of the features of biomolecular recognition and is also the basis for allosteric effects and signal transduction in functional biological systems. However, synthetic receptors with controllable conformational changes are rare. In this article, we present a thorough study on the host–guest chemistry of a conformationally adaptive macrocycle, namely per-O-ethoxyzorb[4]arene (ZB4). Similar to per-O-ethoxyoxatub[4]arene, ZB4 is capable of accommodating a wide range of organic cations. However, ZB4 does not show large amplitude conformational responses to the electronic substituents on the guests. Instead of a linear free-energy relationship, ZB4 foll…

CCDC 1488067: Experimental Crystal Structure Determination

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CCDC 1439185: Experimental Crystal Structure Determination

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CCDC 1938198: Experimental Crystal Structure Determination

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CCDC 1917460: Experimental Crystal Structure Determination

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CCDC 1549337: Experimental Crystal Structure Determination

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CCDC 1021543: Experimental Crystal Structure Determination

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CCDC 2068107: Experimental Crystal Structure Determination

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CCDC 1557843: Experimental Crystal Structure Determination

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CCDC 1429822: Experimental Crystal Structure Determination

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CCDC 915607: Experimental Crystal Structure Determination

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CCDC 1938870: Experimental Crystal Structure Determination

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CCDC 1885475: Experimental Crystal Structure Determination

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CCDC 1986124: Experimental Crystal Structure Determination

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CCDC 1844228: Experimental Crystal Structure Determination

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CCDC 1006725: Experimental Crystal Structure Determination

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CCDC 2060887: Experimental Crystal Structure Determination

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CCDC 2041026: Experimental Crystal Structure Determination

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CCDC 1426136: Experimental Crystal Structure Determination

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CCDC 1837609: Experimental Crystal Structure Determination

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CCDC 1938871: Experimental Crystal Structure Determination

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CCDC 1061111: Experimental Crystal Structure Determination

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CCDC 2109381: Experimental Crystal Structure Determination

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CCDC 1935914: Experimental Crystal Structure Determination

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CCDC 1040206: Experimental Crystal Structure Determination

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CCDC 1551412: Experimental Crystal Structure Determination

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CCDC 2009558: Experimental Crystal Structure Determination

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CCDC 1583131: Experimental Crystal Structure Determination

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CCDC 1045984: Experimental Crystal Structure Determination

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CCDC 1469004: Experimental Crystal Structure Determination

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CCDC 1453056: Experimental Crystal Structure Determination

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CCDC 1992636: Experimental Crystal Structure Determination

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CCDC 1045981: Experimental Crystal Structure Determination

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CCDC 1519435: Experimental Crystal Structure Determination

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CCDC 1901282: Experimental Crystal Structure Determination

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CCDC 1966174: Experimental Crystal Structure Determination

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CCDC 1957981: Experimental Crystal Structure Determination

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CCDC 2106021: Experimental Crystal Structure Determination

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CCDC 2127766: Experimental Crystal Structure Determination

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CCDC 1977492: Experimental Crystal Structure Determination

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CCDC 829593: Experimental Crystal Structure Determination

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CCDC 1533112: Experimental Crystal Structure Determination

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CCDC 2106017: Experimental Crystal Structure Determination

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CCDC 2106015: Experimental Crystal Structure Determination

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CCDC 913147: Experimental Crystal Structure Determination

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CCDC 1478709: Experimental Crystal Structure Determination

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CCDC 957918: Experimental Crystal Structure Determination

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CCDC 1498390: Experimental Crystal Structure Determination

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CCDC 2000981: Experimental Crystal Structure Determination

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CCDC 1407855: Experimental Crystal Structure Determination

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CCDC 1977495: Experimental Crystal Structure Determination

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CCDC 1439186: Experimental Crystal Structure Determination

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CCDC 1056977: Experimental Crystal Structure Determination

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CCDC 913151: Experimental Crystal Structure Determination

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CCDC 945021: Experimental Crystal Structure Determination

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CCDC 2000978: Experimental Crystal Structure Determination

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CCDC 2064892: Experimental Crystal Structure Determination

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CCDC 1577818: Experimental Crystal Structure Determination

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CCDC 1556030: Experimental Crystal Structure Determination

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CCDC 1977494: Experimental Crystal Structure Determination

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CCDC 2069304: Experimental Crystal Structure Determination

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CCDC 1837606: Experimental Crystal Structure Determination

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CCDC 1040201: Experimental Crystal Structure Determination

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CCDC 1895019: Experimental Crystal Structure Determination

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CCDC 1557841: Experimental Crystal Structure Determination

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CCDC 1947525: Experimental Crystal Structure Determination

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CCDC 1479470: Experimental Crystal Structure Determination

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CCDC 1935926: Experimental Crystal Structure Determination

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CCDC 913154: Experimental Crystal Structure Determination

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CCDC 957920: Experimental Crystal Structure Determination

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CCDC 2106020: Experimental Crystal Structure Determination

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CCDC 1963302: Experimental Crystal Structure Determination

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CCDC 1439187: Experimental Crystal Structure Determination

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CCDC 2067947: Experimental Crystal Structure Determination

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CCDC 1550979: Experimental Crystal Structure Determination

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CCDC 216932: Experimental Crystal Structure Determination

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CCDC 1901276: Experimental Crystal Structure Determination

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Bis-urea macrocycles with a deep cavity

Two bis-urea macrocycles with a deep cavity demonstrate an enzyme-like binding, and the influence of dipole alignments on molecular recognition.

CCDC 993789: Experimental Crystal Structure Determination

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CCDC 967819: Experimental Crystal Structure Determination

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CCDC 2000612: Experimental Crystal Structure Determination

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CCDC 1005272: Experimental Crystal Structure Determination

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CCDC 1995533: Experimental Crystal Structure Determination

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CCDC 1411525: Experimental Crystal Structure Determination

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CCDC 1542055: Experimental Crystal Structure Determination

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CCDC 1426935: Experimental Crystal Structure Determination

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CCDC 2000982: Experimental Crystal Structure Determination

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CCDC 2192597: Experimental Crystal Structure Determination

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CCDC 2080292: Experimental Crystal Structure Determination

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CCDC 1970146: Experimental Crystal Structure Determination

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CCDC 1439768: Experimental Crystal Structure Determination

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CCDC 1481998: Experimental Crystal Structure Determination

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CCDC 1985011: Experimental Crystal Structure Determination

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CCDC 2080291: Experimental Crystal Structure Determination

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CCDC 782858: Experimental Crystal Structure Determination

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CCDC 2000986: Experimental Crystal Structure Determination

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CCDC 1053245: Experimental Crystal Structure Determination

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CCDC 1995536: Experimental Crystal Structure Determination

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CCDC 1935915: Experimental Crystal Structure Determination

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CCDC 1006724: Experimental Crystal Structure Determination

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CCDC 2001488: Experimental Crystal Structure Determination

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CCDC 1995534: Experimental Crystal Structure Determination

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CCDC 2080283: Experimental Crystal Structure Determination

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CCDC 1583125: Experimental Crystal Structure Determination

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CCDC 1427937: Experimental Crystal Structure Determination

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CCDC 1532334: Experimental Crystal Structure Determination

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CCDC 1478711: Experimental Crystal Structure Determination

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CCDC 927661: Experimental Crystal Structure Determination

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CCDC 1051459: Experimental Crystal Structure Determination

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CCDC 1408384: Experimental Crystal Structure Determination

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CCDC 1047382: Experimental Crystal Structure Determination

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CCDC 2193615: Experimental Crystal Structure Determination

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CCDC 2080293: Experimental Crystal Structure Determination

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CCDC 1029374: Experimental Crystal Structure Determination

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CCDC 2105108: Experimental Crystal Structure Determination

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CCDC 2225071: Experimental Crystal Structure Determination

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CCDC 1573412: Experimental Crystal Structure Determination

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CCDC 1550977: Experimental Crystal Structure Determination

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CCDC 2106013: Experimental Crystal Structure Determination

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CCDC 2027291: Experimental Crystal Structure Determination

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CCDC 1561541: Experimental Crystal Structure Determination

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CCDC 2242258: Experimental Crystal Structure Determination

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CCDC 1408381: Experimental Crystal Structure Determination

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CCDC 1815760: Experimental Crystal Structure Determination

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CCDC 1821336: Experimental Crystal Structure Determination

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CCDC 1957891: Experimental Crystal Structure Determination

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CCDC 2062095: Experimental Crystal Structure Determination

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CCDC 1426143: Experimental Crystal Structure Determination

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CCDC 2067946: Experimental Crystal Structure Determination

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CCDC 1573312: Experimental Crystal Structure Determination

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CCDC 913161: Experimental Crystal Structure Determination

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CCDC 990707: Experimental Crystal Structure Determination

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CCDC 1514737: Experimental Crystal Structure Determination

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CCDC 1935913: Experimental Crystal Structure Determination

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CCDC 2000983: Experimental Crystal Structure Determination

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CCDC 1452354: Experimental Crystal Structure Determination

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CCDC 1977488: Experimental Crystal Structure Determination

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CCDC 1935929: Experimental Crystal Structure Determination

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CCDC 1005277: Experimental Crystal Structure Determination

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CCDC 1824417: Experimental Crystal Structure Determination

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CCDC 1556033: Experimental Crystal Structure Determination

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CCDC 1958053: Experimental Crystal Structure Determination

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CCDC 1550981: Experimental Crystal Structure Determination

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CCDC 1469006: Experimental Crystal Structure Determination

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CCDC 1519437: Experimental Crystal Structure Determination

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CCDC 1415586: Experimental Crystal Structure Determination

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CCDC 1407240: Experimental Crystal Structure Determination

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CCDC 1006950: Experimental Crystal Structure Determination

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CCDC 782862: Experimental Crystal Structure Determination

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CCDC 1498874: Experimental Crystal Structure Determination

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CCDC 2106022: Experimental Crystal Structure Determination

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CCDC 2106016: Experimental Crystal Structure Determination

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CCDC 1021604: Experimental Crystal Structure Determination

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CCDC 1474771: Experimental Crystal Structure Determination

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CCDC 1901283: Experimental Crystal Structure Determination

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CCDC 1817835: Experimental Crystal Structure Determination

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CCDC 1008273: Experimental Crystal Structure Determination

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CCDC 913150: Experimental Crystal Structure Determination

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CCDC 1575262: Experimental Crystal Structure Determination

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CCDC 2067943: Experimental Crystal Structure Determination

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CCDC 1539541: Experimental Crystal Structure Determination

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CCDC 1935912: Experimental Crystal Structure Determination

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CCDC 1417790: Experimental Crystal Structure Determination

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CCDC 1522088: Experimental Crystal Structure Determination

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CCDC 913155: Experimental Crystal Structure Determination

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CCDC 1053247: Experimental Crystal Structure Determination

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CCDC 1519225: Experimental Crystal Structure Determination

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CCDC 993790: Experimental Crystal Structure Determination

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