Columnar supramolecular architecture of crystals of 2-(4-Iodophenyl)-1,10-phenanthroline derived from values of intermolecular interaction energy

Using results of X-ray diffraction study supramolecular architecture of crystals of 2-(4-iodophenyl)-1,10-phenanthroline has been analyzed on the basis of quantum-chemical calculations of intermolecular interactions energy. It is demonstrated that these crystals have three levels of organization. Molecules form stacked dimers with the highest binding energy (first level). These dimers represent basic unit of infinite columns stabilized by stacking interactions between dimers (second level). The energy of intermolecular interactions between neighbouring stacked columns is very close. This does not allow to figure out any layers in the crystal. Therefore crystals of this compound have columna…

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.

Phenanthroline Ligands with Divergent Pyridine Units

2-Mono- and 2,9-di-substituted 1,10-phenanthrolines with 4-pyridine units attached either via 1,4-phenylene- or 4-ethynyl-phenyl spacers, have been synthesised. The strategy is based on the introduction of 4-trimethylsilylphenyl group(s) at the phenanthroline core with the subsequent ipso-substitution of TMS groups by bromine or iodine and successive Suzuki or Sonogashira reactions with 4-pyridineboronic acid or 4-ethynylpyridine, respectively.

New Molecular Topologies by Fourfold Metathesis Reactions within a Hydrogen-Bonded Calix[4]arene Dimer

A calix[4]arene tetrapentyl ether in the cone conformation substituted at its wide rim by four m-(omega-octenyloxy)phenyl urea groups forms hydrogen-bonded dimeric capsules in dichloromethane/benzene (95:5). Metathesis reaction with Grubbs' catalyst under high-dilution conditions (1.1 x 10(-4) M) followed by hydrogenation leads to a covalent connection of all the urea groups within a dimer. Three topologically different products may be expected in such a reaction: a bis[2]catenane, a doubly bridged monocatenane and a tetrabridged capsule. All three possible reaction products could be isolated in an overall yield up to 60 % for the separated and purified compounds. Their identification was b…

Multiple Catenanes Derived from Calix[4]arenes

A multicatenane is described in which two belts consisting of four annelated rings attached to the wide rims of two calix[4]arenes are interwoven in such a way that each ring of one belt penetrates two adjacent rings of the other belt and vice versa. The key step of the synthesis of this [8]catenane is the exclusive formation of preorganized heterodimers between a multimacrocyclic tetraurea calix[4]arene and an “open-chain” tetraurea calix[4]arene containing eight ω-alkenyl groups. When a tetraurea calix[4]arene containing four alkenyl groups is used, a bis-[3]catenane is formed analogously.

Tetraurea Calix[4]arenes

Orientational preferences of aromatic guests in dimeric capsules of tetraurea calix[4]arenes—MD and NMR studies

Molecular dynamics (MD) simulations have been performed for complexes of a dimeric capsule of a tetraurea calixarene with a series of twelve aromatic guests. A distinct orientational preference and a restriction of the internal mobility was found which depend on the size and electronic properties of the guests. The results are in agreement with the CIS values obtained from (1)H NMR spectroscopic measurements and with complexation selectivities obtained by competition experiments.

Synthesis of huge macrocycles using two calix[4]arenes as templates.

Macrocycles with up to 100 atoms have been synthesised using two calix[4]arenes as templates: first, (3,5-dialkenyloxy)phenyl groups are attached to the wide rim of a calix[4]arene via urea links, then the alkenyl groups are connected via a metathesis reaction using a tetratosylurea calix[4]arene for their correct prearrangement and finally the urea functions are cleaved to detach the newly formed macrocycles.

Calix[4]arene-Based Bis[2]catenanes: Synthesis and Chiral Resolution

The exclusive formation of hydrogen-bonded dimers between tetraaryl and tetratosylurea calix[4]arenes has been used to prepare a series of ten "bisloop" tetraurea calix[4]arenes 3, in which adjacent phenylurea groups are covalently linked through alpha,omega-dioxyalkane chains. This dimerization with tetratosylurea 2 as template preorganizes the alkenyl residues of tetra(m-alkenyloxyphenyl) ureas 1 and enables their selective connection in high yield (up to 95 %) by olefin metathesis followed by hydrogenation. The "bisloop" calixarenes 3 also exclusively form heterodimers with 1. Thus, in a separated metathesis/hydrogenation sequence, a series of 14 cyclic bis[2]catenanes 4, in which two ca…

Guest exchange in dimeric capsules of a tetraurea calix[4]arene in the solid state

A solid powder of hydrogen bonded dimers of a tetraurea calix[4]arene is able to exchange the encapsulated guest in contact with the vapor of a second guest. The molecules of a guest-free powder obtained from a polar solvent cannot rearrange in the solid phase to form new guest-filled capsules under these conditions.

Vierfache [2]Rotaxane von Calix[4]arenen durch Ringschluss

Enhanced thermodynamic and kinetic stability of calix[4]arene dimers locked in the cone conformation.

Wide rim tetraurea derivatives (2a,b) have been prepared from a calix[4]arene rigidified in the cone conformation by two diethyleneglycol ether bridges between adjacent oxygens. In comparison to the analogous tetraurea derivatives (3a,b) of a tetrapentoxy calix[4]arene, 2a,b show an increased thermodynamic stability in mixtures of CDCl(3) and DMSO-d(6). Their kinetic stability as expressed by the rate of guest exchange (benzene or cyclohexane against the solvent benzene-d(6)) is also strongly increased by factors of 30-38. Noticeable differences for the inclusion of selected guests are found.

Compensation of steric demand by cation–π interactions, cobaltocenium cations as guests in tetraurea calix[4]arene dimers

The affinities of ferrocene (2) and the cobaltocenium cation (3+), which have roughly the same size and differ in their charge, towards the inner cavity of the dimeric capsule formed by tetraurea calix[4]arene (1) were studied in C2D4Cl2 solutions. While 3+, which occupies more than 75% of the internal volume of the dimer, is readily encapsulated this is not the case for 2. This is probably due to cation-pi interactions, which operate only between 3+ and the aromatic rings of the calix[4]arene dimer. We found that the affinity of the cobaltocenium cation is higher than that of the tropylium cation (4+) and is only 2-3 times less than that of the tetraethylammoniun cation (5+). From the vari…

2,7-Di-tert-butyl-9,9-dimethyl-4,5-bis(4-tritylanilinocarbonyl)-9H-xanthene methanol trisolvate monohydrate

The title compound, C75H68N2O3·3CH3OH·H2O, was synthesized starting from the corresponding acid and p-tritylaniline. Single crystals were obtained from a methanol solution as a solvate, with three methanol mol­ecules and one water mol­ecule. The solid-state structure proves the existence of an intra­molecular bifurcated hydrogen bond between one amide H atom and the carbonyl and xanthene O atoms. The packing is stabilized by inter­molecular hydrogen bonds.

Template synthesis of multi-macrocycles by metathesis reaction.

Selective heterodimerisation of tetraurea calix[4]arenes containing four or eight ω-alkenyl groups with a tetratosyl urea calix[4]arene has been effectively used to synthesize multi-macrocycles via metathesis reaction.

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 …

Topologically Novel Multiple Rotaxanes and Catenanes Based on Tetraurea Calix[4]arenes

Calix[4]arenes bearing at their wide rim four urea residues easily form hydrogen bonded dimeric capsules. This has been used to preorganise alkenyl functions attached to these urea groups for their controlled connection via metathesis reaction. Multimacrocyclic tetraurea derivatives are thus obtained in excellent yields via heterodimers which are formed exclusively with tetratosylurea derivatives. Heterodimerisation of such bis- and tetraloop tetraureas leads analogously to multicatenanes, or to rotaxanes by stoppering. Huge macrocycles are detached from tetraloop derivatives by cleavage of the urea function.

Template Synthesis of Multi-Macrocycles by Metathesis Reactions.

Vibrational spectroscopy of a tetraureidocalix[4]arene based molecular capsuleElectronic supplementary information (ESI) available: three tables containing fully assigned IR data of tetraureido calix[4]arene 1, its complex with cyclohexane and benzene, and the corresponding model substances 2–5 as well as 1H NMR spectra of the capsules 1·C6H6·1 and 1·C6H12·1 in solution. See http://www.rsc.org/suppdata/p2/b1/b108055p/

Structural models for self-assembled dimers composed of two urea calix[4]arenes which entrap benzene or cyclohexane are developed using Fourier transform infrared (FTIR) spectroscopy. Based on the host–guest ratio determined by 1H NMR spectroscopy in solution, and confirmed for the solid state by a thermogravimetric analysis, it is possible to prove by a comparison of the FTIR data of host, guest, complex and model compounds, that the capsule is held together by a cyclic array of weak and strong hydrogen bonds between the urea units attached at the wide rim of the calixarenes. The dimerization of the two urea units leads to a loss of symmetry, and an averaged C4 symmetrical arrangement is p…

5,11,17,23-Tetranitro-25,26,27,28-tetrapentyloxycalix[4]arene

The mol­ecule of the title compound, C48H60N4O12, is located on a crystallographic twofold rotation axis. It is found in the typical pinched cone conformation. The dihedral angles between the reference plane (defined by the C atoms of the methyl­ene bridges) and the benzene rings are 83.33 (6) and 141.61 (5)°.

Self-Assembled Hydrogen-Bonded Dimeric Capsules with High Kinetic Stability

Guest-Enhanced Kinetic Stability of Hydrogen-Bonded Dimeric Capsules of Tetraurea Calix[4]arenes

Inclusion complexes of self-assembled molecular dimers composed of two tetratolylurea calix[4]arenes show strongly different kinetic stability for different guests. In cyclohexane-d12, half-life ti...

ChemInform Abstract: Tropylium Cation Capsule of Hydrogen-Bonded Tetraurea Calix[4]arene Dimers.

ChemInform Abstract: Vibrational Spectroscopy of a Tetraureidocalix[4]arene Based Molecular Capsule.

Preferred dimerization of tetra-tolyl- and tetra-tosylurea derivatives of flexible and rigidified calix[4]arenes

The dimerization of tetratolyl- and tetratosyl-urea derivatives 1 and 2, derived from a tetrapentoxy calix[4]arene in the cone conformation and of the corresponding tetra-urea derivatives 3 and 4, in which the cone conformation is rigidified by the two crown-3 tethers, have been studied. All six possible equimolar mixtures were examined by 1H NMR using CDCl3 and CD2Cl2 as solvents. While no heterodimers are found for the combinations 1/3 and 2/4 in either solvent, all remaining combinations lead to the (exclusive) formation of heterodimers in CD2Cl2. In CDCl3 heterodimers are only observed for the combinations of 3 with 2 or 4. These results are discussed in terms of entropic and enthalpic …

Tropylium cation capsule of hydrogen-bonded tetraurea calix[4]arene dimers

The interaction between tropylium salts and tetraurea calix[4]arene derivatives (such as 1 and 2) was studied in solution using 1D, 2D, diffusion, VT NMR and UV–visible spectroscopy. It was found that tropylium salts form charge transfer complexes with both the monomers and dimers of the tetraurea calix[4]arene derivatives depending on the experimental conditions. Compound 1 increases dramatically the solubility of tropylium salts in apolar solvents such as C2D4Cl2, CDCl3 and CD2Cl2 by forming the molecular capsule 1·C7H7+·1. In contrast to the benzene capsule of 1, in 1·C7H7+·1 the hydrogen bonds in the equatorial region that hold together the two parts of the dimer change their directiona…

Selective Derivatization of Calix[4]arenes via Amino Groups Attached to the Wide Rim

A new strategy is proposed for the synthesis of tetraether derivatives of calix[4]arenes bearing at the wide rim nitro and phthalimido groups in well defined positions. Since both groups are precursors of amino functions, calix[4]arenes substituted by different N-acylamino residues are easily available in four steps. The essential steps during the synthesis of the precursor consist in the protection of amino groups by the formation of their phthalimides followed by ipso-nitration of the remaining tert-butylphenol ether units. This nitration occurs without side reactions at the phthalimido substituted units, in contrast to simple N-acyl derivatives.

Selbstorganisierte, über Wasserstoffbrücken gebundene dimere Kapseln mit hoher kinetischer Stabilität

Fourfold [2]rotaxanes of calix[4]arenes by ring closure.

Self-assembled dimers with supramolecular chirality

The possibilities to form dimeric capsules with supramolecular chirality from tetraurea calix[4]arenes composed of two different phenolic urea units are discussed in general and demonstrated experimentally for various selected examples.

Rational Synthesis of Multicyclic Bis[2]catenanes

Bis-loop tetraurea calix[4]arene 6 has been prepared by acylation of the wide-rim calix[4]arene tetraamine 1 with the activated bis(urethane) 8 under dilution conditions. Similarly the bis(Boc-protected) tetraamine 2 is converted into the mono-loop derivative 3 which after deprotection and acylation gives the bisalkenyl derivative 5. In apolar solvents this tetraurea calix[4]arene 5 forms regioselectively a single hydrogen-bonded homodimer, from which the bis[2]catenane 10 a is formed in 49 % by a metathesis reaction followed by hydrogenation. Bis-loop derivative 6 forms no homodimers for steric reasons, but a stoichiometric mixture with the open-chain tetraalkenyl derivative 7 a contains e…

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…

ChemInform Abstract: Chirality in Calixarenes and Calixarene Assemblies

Molecular Motions within Self-Assembled Dimeric Capsules with Tetraethylammonium Cations as Guest

Hydrogen-bonded, dimeric capsules of calix[4]arenes substituted at the wide rim by four urea functions show unprecedented dynamic features when a tetraethylammonium cation is included as a guest. The seam of hydrogen bonds C=O...(HN)2C=O in the equatorial region which holds the two calixarene counterparts together changes its directionality fast (at 25 degrees C), while the dimer itself is kinetically stable on the NMR time scale. An energy barrier of deltaG++ = 49.9 kJmol(-1) (Tc 276 K) was estimated for this reorientation from variable-temperature (VT) NMR measurements. Lowering the temperature to about -50 degrees C restricts also the rotation of the encapsulated tetraethylammonium catio…

Wide Rim Urethanes Derived from Calix[4]arenes:  Synthesis and Self-Assembly

[reaction: see text] Calix[4]arenes 4, substituted at the wide rim by four N-tolyl-urethane groups, were synthesized, as well as derivatives 10a,b bearing two or three tolyl-urea groups beside of one or two urethane group(s). In contrast to tetra-tolyl urea 11, the urethane derivatives do not form hydrogen-bonded, dimeric capsules in CDCl3 or benzene-d6, but the dimerization can be induced for the triurea 10b by tetraethylammonium cations as guests. The quantitative formation of heterodimers is observed for all urethanes 4 and 10a,bin benzene-d6 in mixtures with a "tetra-loop" tetraurea 14, while "bisloop" tetraureas 13 require di- or triurea derivatives 10a,b for a clean heterodimerization.

Guest exchange in dimeric capsules formed by tetra-urea calix[4]arenes

Ten tetra-urea calix[4]arene derivatives with different ether residues (methyl, pentyl, benzyl, all combinations of methyl and pentyl, 1,3-dibenzyl-2,4-dipentyl), including also the tetrahydroxy compound and the 1,3-dipentyl ether, were synthesised. Their urea groups were substituted with a lipophilic residue to ensure sufficient solubility in cyclohexane. Thus, kinetics for the exchange of the included guest (benzene) against the solvent (cyclohexane) could be followed by 1H NMR spectroscopy. The apparent first order rate constants decrease with increasing size of the ether residues from methyl to benzyl by more than three orders of magnitude. This can be understood by a decreasing flexibi…

OH–π and halogen–π interactions as driving forces in the crystal organisations of tri-bromo and tri-iodo trityl alcohols

The trityl alcohols bearing three bromine or three iodine atoms at the para-positions of the aromatic units, have been known for more than a hundred years. In our case these compounds have been synthesized in one-pot sequence starting from the 1,4-dihalogenobenzenes via mono-lithiation and the successive reaction with diethylcarbonate. The compounds have been crystallized from different solvent mixtures leading to one structure of bromo- (A) and three structures of iodo trityl alcohols (B–D). The inclusion of dichloromethane (C) or benzene (D) in the crystalline lattices has been observed. In all cases the OH–π and halogen–π (and in one case the halogen-halogen and CH-O weak) contacts play …

Hydrogen bonded calixarene capsules kinetically stable in DMSO.

Half-life times up to 4 days in DMSO at room temperature are observed for the decomposition of dimeric capsules of urea substituted calix[4]arenes held together by a combination of hydrogen bonds, mechanical entanglement and cation–π interactions.