Outer and inner coordination sphere chemistry of polyazacyclophane platinum(II) complexes. Crystal structure of [PtBr4]2(H4L1) · H2O (L1 = 2,6,9,13-tetraaza[14]paracyclophane)

Abstract The interaction of PtCl42− with the new azaparacyclophane 2,5,8,11-tetraaza[12]paracyclophane (L2) has been studied by 1H, 13C and 195Pt NMR spectroscopy. Three different complexes are detected as a function of pH, all of them presenting cis-arrangement of nitrogen donors and chloride anions. In the first one, formed at acidic pH, the central nitrogen atoms of the macrocyclic are coordinating to Pt(II) while the benzylic nitrogens remain protonated. Deprotonation of these nitrogens brings about a reorganisation of the complex, and the platinum is then coordinated by one benzylic nitrogen and the consecutive nitrogen in the macrocycle. This process can be monitored by NMR. Finally, …

A solution study of complex formation between iron(III) and oxalate in dimethylsulphoxide

The complex formation between iron(III) and oxalic acid (ethanedioic acid, H2ox) has been studied by potentiometry in dimethylsulphoxide (dmso) solution. H2ox behaves as a weak diprotic acid in such a solvent, with overall association constants: log βj1=8.551(3) and log βj2=14.242(3) at 25°C and 0.1 Mn-Bu4NClO4. A reliable set of overall stability constants for the iron(III)-oxalato complexes, log β11=13.16(4), log β12=23.66(4) and log β13=30.75(4), have been obtained for the first time under identical conditions. The electrochemical behaviour of such complexes was studied in dmso at a platinum electrode. The coordination ability of oxalate towards iron(III) in dmso and water media is compa…

Homo- and heterobinuclear Cu2+ and Zn2+ complexes of abiotic cyclic hexaazapyridinocyclophanes as SOD mimics

The new receptor 3,7,11,15,19,23-hexaaza-1(2,6)-pyridinacyclotetracosaphane (L1) containing a complete sequence of propylenic chains has been synthesised. The acid–base behaviour and Cu2+ and Zn2+ coordination have been analysed by potentiometric measurements in 0.15 M NaClO4 for L1 and for the related compounds 3,7,11,14,18,22-hexaaza-1(2,6)-pyridinacyclotricosaphane (L2), 3,7,10,13,16,20-hexaaza-1(2,6)-pyridinacycloheneicosaphane (L3) and 3,7,10,12,15,19-hexaaza-1(2,6)-pyridinacycloicosaphane (L4). The crystal structure of [(CuH4L2)(H2O)(ClO4)](ClO4)5·3H2O shows an interesting combination of a metal ion coordinated by the pyridine nitrogen atom and the adjacent amine groups of the chain, …

Expanding the atrane route: Generalized surfactant-free synthesis of mesoporous nanoparticulated xerogels

Abstract A diversity of silica-based and non-silica nanoparticulated mesoporous xerogels have been synthesized from aqueous solution using a surfactant-free strategy, and starting from molecular atrane complexes as precursors. This approach constitutes an extension of the “atrane route” previously described for the surfactant-assisted synthesis of mesoporous materials, and allows us to unify the multiplicity of protocols described for the preparation of conventional xerogels. In fact, we have used exactly the same preparative conditions for obtaining all the compositions reported here. The xerogels synthesized in this way include pure silica (UVM-11), aluminosilicates and titanosilicates (M…

Incorporation of Silica Nanospherical Particles into Epoxy-Amine Crosslinked Materials

Composites of silica nanospheres coated with crosslinked epoxy–amine were synthesised and examined by 29Si-magic-angle-spinning nuclear magnetic resonance spectroscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. The most representative fact is that epoxy-modified nanospheres lost less weight at high temperatures. At temperatures greater than 300°C the loss of weight for epoxy-modified nanospheres was rather lower than for unmodified nanospheres. This helped them to retain their structures, as the loss of weight can have adverse effects on network defects, due to the loss of crosslinks by unit of volume.

Molecular precursors of mesostructured silica materials in the atrane route: A DFT/GIAO/NBO theoretical study

Abstract Quantum chemical calculations using density functional theory have been carried out to investigate two assumed molecular precursors and identified as silatranes (N[OCH2CH2]3Si–OCH2CH2N–(CH2CH2OH)2 and N[OCH2CH2]3Si–OCH2CH2N–(CH2CH2OH)2Na+) which are present in the synthesis of mesoporous silica based material namely “the atrane route”. One of the ways in this synthesis leads to the well-known MCM-41. Additionally, in this work has been also investigated two others molecules such as triethanolamine (TEAH3) and sodatrane which are present in the medium. Gas phase and solution equilibrium geometries of the previous molecules were fully optimized at B3LYP level, modeling solvent effect…

Pore Length Effect on Drug Uptake and Delivery by Mesoporous Silicas

The capability of UVM-7 silicas to work as supports for drug storage and delivery is investigated using ibuprofen as a model. UVM-7 silicas are surfactant-assisted synthesised mesoporous materials displaying a characteristic bimodal pore architecture related to their nanoparticulate texture. Strict control of the drug-charge protocol allows the achievement of high ibuprofen loads, not only because of the availability of intra-nanoparticle mesopores and large textural voids, but also owing to the decrease in pore-blocking effects (with regard to related unimodal mesoporous materials such as MCM-41) achieved through the shortening of the mesopore length. The UVM-7/ibuprofen nanocomposites are…

Enhanced manganese content in Mn-MCM-41 mesoporous silicas

The use of triethanolamine containing complexes of Si and Mn as hydrolytic precursors allows the synthesis of doped mesoporous silicas in which the Mn content can be modulated up to reach a minimum value of the Si/Mn molar ratio of 3. This limit value corresponds to a Mn relative content significantly higher than those reported to date for similar materials (Si/Mn = 6). According to XRD, TEM and porosity data, the mesoporous nature typical of the MCM-41 silicas is retained even for the samples having the highest Mn content.

One‐Pot Synthesis of a New High‐Aluminium‐Content Super‐Microporous Aluminosilicate

A new super-microporous aluminosilicate having a high aluminium content (Si/Al ca. 1) has been prepared through a surfactant-assisted procedure with the use of a commercially available binary precursor (di-sec-butoxyaluminooxytriethoxysilane) as a single source of both Al and Si. The formation of super-micropores is a result of a significant network shrinkage associated with the thermal elimination of the surfactant. This solid has been studied by X-ray powder diffraction, electron microscopy, nuclear magnetic resonance spectroscopy and porosimetry. A preliminary analysis of the acidity and the catalytic activity of the super-microporous solid for the selective catalytic reduction of NOx is…

New complexes of nickel and nickel/cobalt with tetrahydrofuran-2,3,4,5-tetracarboxylic acid, THF(COOH)4. Crystal structures of Ni[THF(COOH)2(COOH)2](H2O)3 and Ni0.7Co0.3[THF(COOH)2(COO)2](H2O)3·H2O and their thermal behaviour

Abstract The reaction of NiCl2·6H2O with tetrahydrofuran-2,3,4,5-tetracarboxylic acid, THF(COOH)4, partially deprotonated by Na2CO3 (1 : 1 metal/ligand molar ratio), yielded Ni[THF(COOH)2(COO)2](H2O)3 (1). The molecular structure of 1 was determined by X-ray diffraction on the monocrystal. The structure consists of a mononuclear neutral unit with the nickel atom coordinated by a [THF(COOH)2(COO)2]2− ligand, which acts as a tridentate ligand, and three water molecules. Direct interaction of NiCl2·6H2O and CoCl2·6H2O (1 : 1 molar ratio) with THF(COOH)4 previously deprotonated by Na2CO3 (1 : 1 metal/ligand molar ratio) gave, by slow evaporation of the solution obtained, green crystals of the n…

ZnO nanoparticles embedded in UVM-7-like mesoporous silica materials: Synthesis and characterization

Abstract ZnO nanodomains embedded in bimodal mesoporous silica (UVM-7) materials with high Zn content (4≤Si/Zn≤30) have been synthesized by an one-pot surfactant-assisted procedure from a hydro alcoholic medium using a cationic surfactant (CTMABr=cetyltrimethylammonium bromide) as structural directing agent, and starting from molecular atrane complexes of Zn and Si as hydrolytic inorganic precursors. This chemical procedure allows optimizing the dispersion of the ZnO particles in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N2 adsorption–desorption isotherms. The small intra-particle mesopore system is due …

Large monolithic silica-based macrocellular foams with trimodal pore system.

Silica-based materials with hierarchical pore systems at three different length scales (small mesopores–large mesopores–macropores) have been prepared through a nanotectonic approach by using mesoporous nanoparticles as building blocks; the resulting materials present a highly accessible foam-like architecture and can be prepared as large monoliths. Huerta Morillo, Lenin Jose, Lenin.Huerta@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Silica-based macrocellular foam monoliths with hierarchical trimodal pore systems

Abstract Silica-based large monoliths exhibiting a trimodal hierarchical pore system have been successfully prepared through a nanotectonic approach starting from sub-micro/nanometric mesoporous particles (as building blocks), and using a polyurethane foam as macrotemplate. Large trimodal pieces with macrocellular like interconnected macropores in the micrometer range are a mineralized replica of the polyurethane foam. Textural large-mesopores/macropores (in the 20–70 nm range) have their origin in the inter-particle voids. The small intra-particle mesopore system (with pore diameters around 2–3 nm) is due to the supramolecular templating effect of the surfactant.

Synthesis, characterization and a voltammetric study of (Bu4N)2[Mo2Br6]. Oxidation-reduction mechanism of related compounds

The synthesis and characterization of (Bu4N)2[Mo2Br6], obtained from Mo(CO)6, (Bu4N)Br and 1,2-dibromoethane, is described. The electrochemical behaviour of [Mo2Br6]−2 and related species is studied, and an oxidation-reduction mechanism is proposed.

Electrochemical study of dinuclear ruthenium(II)—arene compounds: Electrogeneration of Ru(II)—Ru(I) species

Abstract The preparation and characterization of Ru(II)—arene compounds [{RuCl2(p-cym)}2(μ-L-L)] where p-cym = p-MeC6H4CHMe2; and L-L = diphenylphosphinomethane (I), 1,1′-bisdiphenylphosphinoferrocene (II), pyrazine (III) and 4,4′-bipyridine (IV), are described. Electrochemical data for these compounds obtained by cyclic voltammetry and coulometry are reported. The electrochemical reduction of compounds I or II yields ruthenium(O) species. However, compounds III or IV containing ligands with delocalized Π orbitals undergo one-electron reduction. The ESR signal detected during the electrolysis of compounds III or IV is consistent with one delocalized electron through the whole dinuclear unit.

Orthometallation reactions of rhodium compounds containing orthohaloarylphosphines

The reaction of RhCl3·.3H2O with a 3-molar proportion of P(o-ClC6H4)Ph2, (PCCl) at room temperature gives RhCl(PCCl)2 (1), in high yield. Reaction of [Rh(cot)2Cl]2, (cot = cyclooctene), with PCCl, sol12 molar ratio, also gives compound 1. Refluxing of a solution of 1 in 96% ethanol gives RhCl2(PC)(η2-PCCl), [PC  (C6H4)PPh2] (2). Complex 1 reacts with CO to give RhClCO(PCCl)2 (3). 31P NMR studies reveal that 1 exhibits a fluxional behaviour in solution in the temperature range −50 to 0 °C. The low temperature spectrum is consistent with the formulation RhCl(η2-PCCl)(η1-PCCl). In cyclic voltammetry complex 2 shows two two-electronic reduction processes, at −0.98 and −1.56 V. Electrochemical …

Thermodynamic and kinetic studies on the Cu2+ coordination chemistry of a novel binucleating pyridinophane ligandElectronic supplementary information (ESI) available: Table S1: observed rate constants for the acid-promoted decomposition of Cu2+ complexes with ligand L. Table S2: observed rate constants for the acid-promoted decomposition of Cu2+ complexes with macrocycle L1. Fig. S1: Variation of some selected 13C chemical shifts as a function of pH. See http://www.rsc.org/suppdata/dt/b2/b209013a/

The synthesis and coordination chemistry of the novel pyridine-functionalized ligand 2,6,9,12,16-pentaaza[17]-(2,6)pyridinophane (L1) is described. The compound behaves as a hexaprotic base in aqueous solution. NMR studies indicate a protonation pattern in which the sp2 pyridine nitrogen (N(py)) does not undergo a net protonation although it is involved in formation of hydrogen bonds. L1 forms mono and binuclear hydroxylated complexes. The crystal structure of [CuL1](ClO4)2 shows a square planar coordination for Cu2+ with the pyridine and the three central nitrogens of the chain forming the vertices of the square. The benzylic nitrogens could be occupying the axial positions of a strongly a…

Interactions of metal ions with two quinolone antimicrobial agents (cinoxacin and ciprofloxacin)

Several novel metal-quinolone compounds have been synthesized and characterized by analytical, spectroscopic and X-ray diffraction methods. The crystal structure of the four compounds, Na(2)[(Cd(Cx)3)(Cd(Cx)3(H2O))].12H2O, [Co(Cp)2(H2O)2].9H2O, [Zn(Cp)2(H2O)2].8H2O and [Cd(HCp)2(Cl)2].4H2O, is presented and discussed: HCx=1-ethyl-1,4-dihydro-4-oxo(1,3)-dioxolo(4,5-g)cinnoline-3-carboxylic acid and HCp=1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinoline carboxylic acid. In all these compounds the quinolone acts as a bidentate chelate ligand that binds through one carboxylate oxygen atom and the exocyclic carbonyl oxygen atom. Complexes of ciprofloxacin were screened for th…

Electrochemical study on a tricyclic 1,1,1-tricar-bonyl-2,3-1 diazaferrole derivative. II. Activation of carbon monoxide replacement by electron transfer processes

Etudes, par voltammetrie cyclique, de la reduction electrochimique du complexe de diazaferratricyclodecene, en presence de P(OMe) 3

Hydrogen and copper ion-induced molecular reorganizations in scorpionand-like ligands. A potentiometric, mechanistic, and solid-state study.

Two aza scorpionand-like macrocycles (L2 and L3) have been prepared. L2 consists of a tren amine with two of its arms cyclizized with a 2,6-bis(bromomethyl)pyridine. In L3, the remaining pendant arm has been further functionalized with a fluorophoric naphthalene group. X-ray data on the compounds [H(L3)]ClO4.H2O (1) and [H3(L3)](H2PO4)3.H2O (2) as well as solution studies (pH-metry, UV-vis, and fluorescence data) show the movement of the pendant arm as a result of the protonation degree of the macrocycles and of the formation of intramolecular hydrogen bonds. X-ray data on the complexes [Cu(L2)](ClO4)2]2.H2O (3) and [Cu(L3)](ClO4)2 (4) and solution studies on Cu2+ coordination show the impl…

Improving epoxide production using Ti-UVM-7 porous nanosized catalysts

Nanosized Ti-UVM-7 materials with a hierarchical system of pores at two different length scales have been prepared through a one-pot procedure by using a simple template agent; the catalytic activity and selectivity of the resulting materials in bulky olefin epoxidation by organic peroxides are the highest reported to date.

Mesoporous aluminum phosphite

Abstract High surface area pure mesoporous aluminum-phosphorus oxide-based derivatives have been synthesized through an S+I− surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from aluminum atrane complexes and phosphoric and/or phosphorous acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from mesoporous aluminum phosphate (ALPO) up to total incorporation of phosphite entities (mesoporous aluminum phosphite), which results in a gradual evolution of the acid…

Nanoparticulated Silicas with Bimodal Porosity: Chemical Control of the Pore Sizes

Nanoparticulated bimodal porous silicas (NBSs) with pore systems structured at two length scales (meso- and large-meso-/macropores) have been prepared through a one-pot surfactant-assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The final bulk materials are constructed by an aggregation of pseudospherical mesoporous primary nanoparticles process, over the course of which the interparticle (textural) large pore system is generated. A fine-tuning of the procedural variables allows not only an adjustment of the processes of nucleation and growth of the primary nanoparticles but also a modulation of their subseque…

Self-assembly of 3,5-bis(ethoxycarbonyl)pyrazolate anions and ammonium cations of β-phenylethylamine or homoveratrylamine into hetero-double-stranded helical structures

Hydrogen-bonded double-stranded hetero-helices are formed when reacting sodium 3,5-bis(ethoxycarbonyl)pyrazolate with beta-phenethylammonium or homoveratrylammonium chloride, in which one of the strands is defined by the ammonium cations and the other one by the pyrazolate anions.

Molecular structure of the compound [Rh2(O2CCH3)3{(C6H4)P(BrC6H4-1,2)(C6H5)} · (HO2CCH3)2].Kinetic study of the exchange reaction of acetate groups with CD3CO2D

Abstract The compound [Rh 2 (O 2 CCH 3 ) 3 {(C 6 H 4 )P(BrC 6 H 4 -1,2) (C 6 H 5 )} · (HO 2 CCH 3 ) 2 ] has been isolated in high yield from the thermal reaction of dirhodium tetraacetate and the phosphine P(BrC 6 H 4 -1,2) (C 6 H 5 ) 2 in acetic acid. The structure of this compound has been determined by X-ray diffraction; it crystallizes in the P 1 (triclinic) space group and contains three acetate groups bridging a Rh 2 4+ unit the RhRh distance being 2.432(1)A; the fourth bridging ligand is an ortho -bromophenyldiphenylphosphine metallated at one of the ortho positions of the unsubstituted phenyl rings. Two molecules of acetic acid occupy the axial coordination positions. Stepwise exch…

Hydrogen and Copper Ion Induced Molecular Reorganizations in Two New Scorpiand-Like Ligands Appended with Pyridine Rings

The synthesis of two new ligands constituted of a tris(2-aminoethyl)amine moiety linked to the 2,6 positions of a pyridine spacer through methylene groups in which the hanging arm is further functionalized with a 2-pycolyl (L1) or 3-pycolyl (L2) group is presented. The protonation of L1 and L2 and formation of Cu(2+) complexes have been studied using potentiometric, NMR, X-ray, and kinetic experiments. The results provide new information about the relevance of molecular movements in the chemistry of this kind of so-called scorpiand ligand. The comparison between these two ligands that only differ in the position of the substituent at the arm reveals important differences in both thermodynam…

Ordered Mesoporous Silicon Oxynitrides

Reaction of Rh2(μ2-O2CCH3)3[μ2-(C6H4)PMePh](HO2CCH3)2 with triphenylphosphine: rearrangement of the metalated PMePh2 ligand and formation of a compound with a diphenylphosphinomethanide group in (P,C) coordination; crystal structure of [Rh2(μ2-O2CCH3)2{μ2-(CH2)PPh2}- {μ2-(C6H4)PPh2}(PPh3)]·2CH2Cl2

The reaction of [Rh2(μ2-O2CCH3)3{μ2-(C6H4)PMePh}] (1) in CHCl3 with one mole of PPh3 gives the two phosphine monoadducts, which are in rapid equilibrium above −40 °C. After 6 h at room temperature this mixture gives [Rh2(μ2-O2CCH32{μ2-(C6H4)PMePh}{μ2-(C6H4)PPh2}](HO2CCH3)2 (3), a doubly metalated compound with a head-to-head configuration. 1 reacts with two moles of PPh3, forming the bis-adduct 1.P2, which at 10 °C gives a mixture 3, in the form of its phosphine adduct 3.P, and [Rh2(μ2-O2CCH3)2{μ2-(CH2)PPh2}{μ2- (C6H4) PPh2}(PPh3)] (2). It is confirmed that 3.P is not the kinetic product in the reaction from 1.P2 to 2. The structure of [Rh2(μ2-O2CCH3)2{μ2-(CH2)PPh2}{μ2-(CP6H4) PPh2} (PPh3)]…

Electrochemical studies on organometallic compounds—xx. Electrogeneration of an unusual organometallic derivative of ruthenium(I)

Abstract The two-electron reduction of dinuclear ruthenium complexes [RuCl 2 (η 6 - p -cymene)] 2 ( p -cymene = p -CH 3 C 6 H 4 CH(CH 3 ) 2 ] give the corresponding relatively stable ruthenium(I) dimer derivative. The same species can also be obtained by electrochemical reduction of the cationic complexes [(η 6 - p -cymene)Ru(μ-Cl) 3 Ru(η 6 - p -cymene)]PF 6 . A redox mechanism is proposed.

Synthesis and electrochemical study of a new doubly-metallated compound with the ferrocene-labelled phosphine PPh2(C5H4)Fe(C5H5)

Abstract Direct reaction of the metalled compound Rh 2 (μ 2 -O 2 CCH 3 ) 3 [μ 2 -(C 6 H 4 ) PPh 2 ]·(H 2 O) 2 with PPh 2 Fc [Fc = (C 5 H 4 )Fe(C 5 H 5 )] in chloroform solution yields the corresponding mono-adduct Rh 2 (O 2 CCH 3 ) 3 [(C 6 H 4 )PPh 2 ]·(PPh 2 Fc) ( 1 ), which has been characterized by 31 P NMR spectroscopy. Photochemical irradiation of 1 in chloroform gives the compound Rh 2 (μ-O 2 CCH 3 ) 2 (η 2 -O 2 CCH 3 )[μ 2 -(C 6 H 4 )PPh 2 ][PPh 2 Fc]·(H 2 O) ( 2 ) in practically quantitative yield. Compound 2 , by thermal treatment in chloroform solution, yields cleanly the doubly-metallated compound Rh 2 (μ 2 -O 2 CCH 3 ) 2 [μ 2 -(C 6 H 4 )PPhFc][μ 2 -(C 6 H 4 )PPh 2 ]·(H 2 O) 2 ( …

The First Pure Mesoporous Aluminium Phosphonates and Diphosphonates − New Hybrid Porous Materials

Organophosphorus moieties have been incorporated into mesoporous ALPOs through a one-pot surfactant-assisted procedure leading, for the first time, to periodic mesoporous aluminium phosphonates and diphosphonates. The number of organic groups on the surface or in the network can be modulated continuously up to the maximum incorporation level of the respective organophosphorus entities (100 %). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Synthesis of ruthenium(II) compounds with ortho-oxypyridinate ligands (hp). Crystal structure characterization of [Ru(η6-p-CH3C6H4CH(CH3)2)Cl(hp)]

Abstract The reaction of [Ru(η6-p-cymene)Cl2]2 (p-cymene = p-CH3C6H4CH(CH3)2) with Nahp in THF yields [Ru(η6]-p-cymene)Cl(hp)] (1). The crystal structure of (1) has been determined by X-ray methods. (1) crystallizes in the space group Pbca, with a = 16.629(2), b = 10.201(3), c = 17.752(2) A. The compound contains one coordinated arene group, one chlorine and one hp group in a chelating coordination mode. The reaction of (1) with Aghp yields [Ru(η6-p-cymene)(hp)2] (2). The 13C NMR spectrum at - 70°C is consistent with a structure Ru(η6-p-cymene)(η2-hp)(η1-hp). At room temperature a rapid interconvertion between the two hp ligands occurs according to the observed 1H and 13C NMR spectra.

Interactions of metal ions with a 2,4-diaminopyrimidine derivative (trimethoprim)

The interaction of copper (II), zinc(II) and cadmium(II) with Trimethoprim (2,4-diamino-5-(3',4',5'-trimethoxybenzyl) pyrimidine) has been studied. The crystal structures of [Zn(Trim)2Cl2] (2) and [Cd(Trim)Cl2(CH3OH)]n (4) are reported. Compound (2) exhibits a distorted tetrahedral environment around the metal center and crystallizes in the triclinic space group P1 with a=10.2397(6), b=10.4500(6), c=16.3336(16) A, alpha=96.141(8), beta=106.085(5), gamma=96.551(5) degrees and Z=2. In complex (4), the Cd(II) centers are bridged sequentially by two chlorine ions to form infinite chains and present a six-coordinated environment; the compound crystallizes in the monoclinic P2(1)/C space group wi…

Thermodynamic and fluorescence emission studies on chemosensors containing anthracene fluorophores. Crystal structure of {[CuL1Cl]Cl}2·2H2O [L1 = N-(3-aminoprophyl)-N′-3-(anthracen-9-ylmethyl)aminopropylethane-1,2- diamine]

The co-ordination capabilities toward hydrogen ions, Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ of the novel receptor 2,6,9,13-tetraaza[14](9,10)anthracenophane (L) and of its open-chain counterpart N-(3-aminopropyl)-N′-3-(anthracen-9-ylmethyl)aminopropylethane-1,2-diamine (L1) is described. Stepwise protonation constants of the cyclic receptor (L) are lower than those of the open-chain receptor (L1) . Quenching effects of the fluorescence emission occur upon first and second deprotonation of L and upon second deprotonation of L1. Stability constants of the Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ complexes follow the Irving–Williams trend and are intermediate between those of triethylenetetraamine with termin…

Layered-Expanded Mesostructured Silicas: Generalized Synthesis and Functionalization

Mesostructured layered silicas have been prepared through a surfactant-assisted procedure using neutral alkylamines as templates and starting from atrane complexes as hydrolytic inorganic precursors. By adjusting the synthetic parameters, this kinetically controlled reproducible one-pot method allows for obtaining both pure and functionalized (inorganic or organically) lamellar silica frameworks. These are easily deconstructed and built up again, which provides a simple way for expanding the interlamellar space. The materials present high dispersibility, which results in stable colloidal suspensions.

Dopamine interaction with a polyamine cryptand of 1H-pyrazole in the absence and in the presence of Cu(ii) ions. Crystal structure of [Cu2(H−1L](ClO4)3·2H2O

The crystal structure of the binuclear Cu2+ complex [Cu2(H−1L)](ClO4)3 ·2H2O of the cryptand L = 1,4,7,8,11,14,17,20,21,24,29,32,33,36-tetradecaazapentacyclo[12.12.12.1 6,9.119,22,1,31,34]hentetraconta-6,9(41), 19(40), 21,31,34(39)-hexaene is presented; evidence for the formation in solution of binary L–dopamine and ternary Cu2+–L–dopamine complexes is presented.

Towards the Loewenstein limit (Si/Al = 1) in thermally stable mesoporous aluminosilicates

The use of complexing agents to generate polynuclear precursor species containing both Al and Si allows the synthesis of thermally stable mesoporous aluminosilicates including solely tetrahedrally coordinated aluminium, in which the Si/Al ratio can be modulated down to a minimum Si/Al value of 1.06(4). Cabrera Medina, Saul, Saul.Cabrera@uv.es ; El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Silica-based powders and monoliths with bimodal pore systemsElectronic supplementary information (ESI) available: UV–Vis spectrum of sample 3. See http://www.rsc.org/suppdata/cc/b1/b110883b/

Porous pure and doped silicas with pore sizes at two length scales (meso/macroporous) have been prepared and shaped both as powders and monoliths through a one-pot surfactant assisted procedure by using a simple template agent and starting from atrane complexes as inorganic precursors.

CuIIand ZnIICoordination Chemistry of Pyrazole‐Containing Polyamine Receptors − Influence of the Hydrocarbon Side Chain Length on the Metal Coordination

The synthesis of a new macrocyclic receptor (L 4 ) containing two 3,5-dimethylpyrazole units connected by dipropylenetriamine bridges is reported for the first time; pH-metric titrations indicate that L 4 shows six protonation steps in the pH range 2-11. In the absence of metal ions, the pyrazole moieties are not involved in acid-base processes in this pH range. Addition of Cu I I and Zn I I results in deprotonation of the pyrazole moieties which act as bis(monodentate) η 1 :η 1 ligands. This induced deprotonation occurs at higher pH values than in the complexes of the analogous ligand containing diethylenetriamine bridges (L 1 ). The crystal structures of [Cu 2 (H - 2 L 4 )](ClO 4 ) 2 and …

High‐Zirconium‐Content Nano‐Sized Bimodal Mesoporous Silicas

Silica-based nanoparticulated bimodal mesoporous materials with high Zr content (43 ≥ Si/Zr ≥ 4) have been synthesized by a one-pot surfactant-assisted procedure from a hydroalcoholic medium using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes of Zr and Si as hydrolytic inorganic precursors. This preparative technique allows optimization of the dispersion of the Zr guest species in the silica walls. The bimodal mesoporous nature of the final high surface area nano-sized materials is confirmed by XRD, TEM, and N2 adsorption–desorption isotherms. The small intraparticle mesopore system (with pore sizes…

CO2 Fixation by Cu2+ and Zn2+ complexes of a terpyridinophane aza receptor. Crystal structures of Cu2+ complexes, pH-metric, spectroscopic, and electrochemical studies.

The synthesis of the terpyridinophane-type polyamine 2,6,9,12,16-pentaaza[17]-(5,5' ')-cyclo-(2,2':6',2' ')-terpyridinophane heptahydrobromide tetrahydrate (L.7HBr.4H2O) is described. L presents six protonation constants with values in the range 9.21-3.27 logarithmic units. L interacts with Cu2+ and Zn2+ forming in both cases, neutral, protonated, and hydroxylated mono- and binuclear complexes whose constants have been calculated by potentiometry in 0.15 M NaClO4 at 298.1 K. The crystal structures of the compounds [Cu(HL-carb)(H2O)](ClO4)3.2H2O (1) and [Cu2(H2L)(CO3)]2(ClO4)8.9H2O (2) have been solved by X-ray diffraction. In 1, the metal center presents square pyramidal geometry. The base …

Cu2+-Induced formation of cage-like compounds containing pyrazole macrocycles

The crystal structure of the complex [Cu4(H22L)2(H2O)2- (ClO4)2](ClO4)2·2H2O where L is a new pyrazole ligand containing 1,5-diaminopentane spacers represents a new form of obtaining metal ion-induced inorganic–organic cages. Escarti Alemany, Francisco, franesa@alumni.uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Garcia-España Monsonis, Enrique, Enrique.Garcia-Es@uv.es

Scale-up low-cost synthesis of bimodal mesoporous silicas

Porous pure and doped silicas with pore sizes at two length scales (meso/macroporous) have been prepared through a large scale one-pot surfactant assisted reproducible procedure by using a simple template agent and starting from non-expensive sodium silicate as silicon source. Together with the relative low-cost of the reagents we have used, the simplicity of this method, which moreover is scalable and provides high yields, could be a strong argument for considering its suitability for the production of bimodal porous silicas. Additionally, we present a simple chemical scheme that allows directing the synthesis towards different related materials including both bimodal nanoparticulated meso…

One‐Pot Synthesis of Superparamagnetic CoO‐MCM‐41 Nanocomposites with Uniform and Highly Dispersed Magnetic Nanoclusters

Superparamagnetic CoO-MCM-41 mesoporous nanocomposites, with variable cobalt amounts, in the form of well-dispersed CoO-like clusters, were prepared in a large compositional range by a one-step reproducible procedure employing co-hydrolysis and co-condensation of the inorganic precursors in a water/triethanolamine medium. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Theoretical study of oligomeric alumatranes present in the chemistry of materials from micro to mesoporous molecular sieves and alumina composites

Quantum chemical calculations using density functional theory have been carried out to investigate molecular precursors based on alumatranes which are one of the components with silatranes for the preparation of mesoporous aluminosilicate materials. In the same way, some oligomeric alumatranes of this study take part in chemical syntheses related to materials such as zeolites and alumina composite. Gas phase and solution equilibrium geometries of the alumatrane precursors were fully optimized at B3LYP level, modeling solvent effects using a self-consistent reaction field (SCRF). From these optimized geometries, calculations of the 1 H, 13 C and 27 Al NMR chemical shifts at GIAO/B3LYP/6-31G(…

Bases for the synthesis of nanoparticulated silicas with bimodal hierarchical porosity

Porous silicas with pore sizes at two length scales (meso and large meso/macroporous) have been prepared through a one-pot surfactant assisted procedure by using a simple template agent and starting from silicon atrane complexes as hydrolytic inorganic precursors. The special organization of these bimodal porous silicas can be related to the nanometric character of their constituent mesoporous particles. Whereas the small intra-particle mesopore system is generated by the templating effect of the surfactant, the large pore system is defined by inter-particle voids. We have studied the effect of different procedural parameters on the small pore system and also on the nucleation and growth of…

Electrochemical study on (NN)Fe3 (CO)9 ((NN) = 2,3-diazanorbornene) and related compounds. A new example of activation of carbon monoxide replacement by electron transfer.

Abstract The compound (NN)Fe 3 (CO) 9 ( 1 ) in tetrahydrofuran undergoes two reversible one-electron reduction processes in cyclic voltammetry at the platinum electrode. A rapid electron transfer-catalyzed reaction occurs when 1 is reduced in the presence of L (L = P(OMe) 3 ) and this gives (NN)Fe 3 (CO) 8 L ( 2 ), quantitatively. Only an electron-induced nucleophilic substitution is observed for compound 2 under the same conditions, yielding (NN)Fe 3 (CO) 7 L 2 , which undergoes a similar reaction but with much lower efficiency, to give (NN)Fe 3 (CO) 6 L 3 .

Potentiometric and spectroscopic studies of transition-metal ions complexes with a quinolone derivative (cinoxacin). Crystal structures of new Cu(II) and Ni(II) cinoxacin complexes

Abstract The interaction of cobalt(II), nickel(II), copper(II), and zinc(II) with Cinoxacin (HCx = 1-ethyl-1,4-dihydro-4-oxo(1,3)dioxolo(4,5-g)cinnoline-3-carboxylic acid), a 4-quinolone derivative, has been studied at metal/ligand ratios of 1:1-1:3 by means of pH-metric, spectrophotometric, and ESR methods. The formation constants have been determined and the stereochemistry for the metal ions in the species present in aqueous solutions (at 37 ± 0.1°C and I = 0.1 mol dm −3 NaCl) is discussed. In all the studied systems, complexes with different stoichiometric ratios, in which cinoxacin acts both as neutral and deprotonated ligand, are formed. The anomalous sequence of the stepwise stabilit…

CO2 Fixation by Copper(II) Complexes of a Terpyridinophane Aza Receptor

CO2 is fixed by a Cu2+ complex of a macrocyclic terpyridinophane ligand forming a carbamate group. Several features of the structure mimic the enzyme rubisco.

Coordination behavior of sulfathiazole. Crystal structure of [Cu (sulfathiazole) (py)3Cl] superoxide dismutase activity

Abstract The preparation, spectroscopic, magnetic properties, and crystal structure of [Cu(stzxpy) 3 Cl] (stz − stands for the deprotonated form of sulfathiazole, 4-amino-N-2-thiazolylbencenosulfonamide) are reported. Crystals are orthorhombic, space group Pbca, with cell constants a = 15.834(2), b = 17.512(4), and c = 18.79(2) A, and Z = 8. The structure was solved and refined to R = 0.041 (R W = 0.040). The structure consists of mononuclear units linked via hydrogen bonds to form the tridimensional pyramid. The geometry of CuN3N*NCl chromophore is distorted square-pyramid. The superoxide-dismutase mimetic activity of the compound is measured and compared with those of the SOD enzyme, the …

Spectroscopic, Magnetic, and Electrochemical Studies of a Dimeric N-Substituted-Sulfanilamide Copper(II) Complex. X-ray and Molecular Structure of the Cu(2)(sulfathiazolato)(4) Complex.

A copper(II) complex of formula Cu(2)(stz)(4) (stz(-) = sulfathiazolato) has been synthesized and characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic system, space group P2(1)cn with a = 10.595(7) Å, b = 14.274(3) Å, c = 29.65(1) Å, and Z = 4. The structure consists of dinuclear copper(II) units which contain four sulfathiazolato ligands bridging the metal ions through a nonlinear NCN group. The copper atoms are four-coordinated, the chromophore being CuN(4). The Cu.Cu bond distance is 2.671(2) Å. Magnetic susceptibility data in the temperature range 7-300 K show the occurrence of intramolecular antiferromagnetic coupling with 2J = -61.5 cm(-1). …

Synthesis of orthometallated rhodium(III) compounds. Crystal structures of [RhCl2{η2(C6H4)PPh2}(η2-dppm)] and [RhCl{η2(C6H4)PPh2}(η1-PCCl)(phen)] (SbF6)·CH2Cl2 (dppm=bis(diphenylphosphino)methane; PCCl=P(o-ClC6H4)Ph2; phen=1,10 phenanthroline)

Abstract Neutral and cationic rhodium(III) metallated compounds containing a four-membered ring are prepared by different synthetic methods: (i) from rhodium(I) compounds that contain the ligand P( o -ClC 6 H 4 )PPh 2 , by 2c-2e intramolecular oxidative addition; (ii) from metallated dirhodium(II) compounds; (iii) by ligand substitution in [RhCl 2 {η 2 -(C 6 H 4 )PPh 2 }{η 2 -P( o -ClC 6 H 4 )Ph 2 }]. The crystal structures of [RhCl 2 {η 2 -(C 6 H 4 )PPh 2 }(η 2 -dppm)] ( 2 ) and of the dichloromethane solvate of [RhCl{η 2 -(C 6 H 4 )PPh 2 }{η 1 -P( o -ClC 6 H 4 )Ph 2 }(phen)](SbF 6 ) ( 11 ) have been determined by X-ray diffraction methods. In both complexes the Rh atom is in the distorted…

Copper(ii) and Zn(ii) coordination chemistry of tetraaza[n]cyclophanes

The acid–base behaviour and Zn2+ and Cu2+ metal coordination chemistry of the novel orthocyclophane ligands 2,5,8,11-tetraaza[12]orthocyclophane (L2) and 2,5,9,12-tetraaza[13]orthocyclophane (L3) and metacyclophane 2,5,8,11-tetraaza[12]metacylophane (L1) are studied. Important differences in the chemistry of these compounds are found depending on the substitution of the aromatic ring. The ortho derivatives are much more basic in their first two protonation steps while the metacyclophane presents much larger constants in the third and fourth protonation stages. The crystal structure of the picrate salt of [H2L3]2+ shows an alternate disposition of the protons in the molecule with formation o…

Biomimetic chitosan-mediated synthesis in heterogeneous phase of bulk and mesoporous silica nanoparticles

Both bulk and mesoporous silica nanoparticles can be obtained in the form of granular aggregates using chitosan flakes as additive under very soft biomimetic reaction conditions. Puchol Estors, Victoria, Victoria.Puchol@uv.es ; El Haskouri, Jamal, Jamal.Haskouri@uv.es ; Latorre Saborit, Julio, Julio.Latorre@uv.es ; Beltran Porter, Aurelio, Aurelio.Beltran@uv.es ; Beltran Porter, Daniel, Daniel.Beltran@uv.es ; Amoros del Toro, Pedro Jose, Pedro.Amoros@uv.es

Synthesis of new orthometallated iridium(III) compounds by chemical and electrochemical methods

Abstract Replacement of one phosphine ligand in IrCl 3 (η 2 -PCBr)(η 1 -PCBr) ( 1 ) (PCBr = P( o -BrC 6 F 4 )Ph 2 ), by various P-donor ligands has given compounds of stoichiometry IrCl 3 (η 2 -PCBr)L ( 3 : L = PMePh 2 ; 4 : L = P( p -MeC 6 H 4 ) 3 ; 5 : L = P(OMe) 3 , 6 : L = P(OPh) 3 ). All of these show two irreversible reduction peaks in the range −1.1, −1.3 and ca. −2.0 V. The electrochemical reduction of compound 1 at −1.5 V (at 0°C) leads to a very reactive iridium(I) species, probably IrCl(PCBr) 2 , which undergoes intramolecular orthometallation at room temperature. Three compounds are obtained as the results of this chemical conversion: IrBr 2 (PC)(PCBr) ( 7 ), IrCl 2 (PC)(PCBr) (…

Superoxide dismutase activity of ternary copper complexes of sulfathiazole and imidazole derivatives. Synthesis and properties of [CuL2(R-Him)2] [HL=4-amino-N-(thiazol-2-yl)benzenesulfonamide, R-Him=4-methylimidazole, 4,4-dimethylimidazoline or 1,2-dimethylimidazole]. Crystal structure of [CuL2(4,4-dimethylimidazoline)2]

Abstract New ternary copper(II) complexes of sulfathiazole (4-amino-N-(thiazol-2-yl)benzenesulfonamide)(HL) and methyl imidazole derivatives have been synthesised and characterised. The crystal structure of the complex [CuL2(4,4-dmHim)2] (1) [4,4-dmHim=4,4-dimethylimidazoline] has been determined. The copper centre has a quasi regular square planar environment with Cu-nitrogen bond lengths ranging from 1.952 to 2.010 A. From the spectroscopic properties of the complexes [CuL2(1,2-dmHim)2] (2) [1,2-dmHim=1,2-dimethylimidazole] and [CuL2(4-mHim)2] (3) [4-mHim=4-methylimidazole] a distorted tetragonal octahedral geometry is deduced. The compounds showed SOD mimetic activity in fact, a low conc…

New strategies in the development of polynuclear complexes. Crystal structure of the tetranuclear copper(II) complex [Cu4(L1)2(OH)4Cl2(H2O)2]2(H3O2)(ClO4)2Cl·2H2O (L1=2,5,8,11-tetraaza[12](1,4)naphthalenecyclophane)

Abstract The preparation and interaction of the new polyaza[n]naphthalenophanes 2,5,8,11-tetraaza[12](1,4)naphthalenophane (L1) and 2,6,9,13-tetraaza[14](1,4)naphthalenophane (L2) with hydrogen ions and Cu2+ is described. The crystal structure of the new tetranuclear copper(II) complex [Cu4(L1)2(OH)4Cl2(H2O)2]2(H3O2)(ClO4)2Cl·2H2O (L1=2,5,8,11-tetraaza[12](1,4)naphthalenophane) is presented and discussed. A variety of intra- and intermolecular forces contribute to the particular organisation of the crystal. The solution studies indicate the formation of similar tetranuclear species for L1 while for L2 just mononuclear 1:1 species are detected.

Small Azaparacyclophanes as Potential Selective Scavengers of Mercury. Crystal Structure of the Complex Hg2(L1)Cl4 (L1 = 16,17,19,20-Tetramethyl-2,6,9,13-tetraaza[14]paracyclophane)

Supramolecular capping-ligand effect of lamellar silica mesostructures for the one-pot synthesis of highly dispersed ZnO nanoparticles

ZnO?SiO2 lamellar nanocomposites with high zinc content (5?Si/Zn?50) have been synthesized through a one-pot surfactant-assisted procedure from aqueous solution and starting from molecular atrane complexes of Zn and Si as inorganic hydrolytic precursors. This approach allows optimization of the dispersion of the ZnO nanodomains in the silica sheets. The nature of the layered silica materials has been confirmed by x-ray diffraction. Spectroscopic (ultraviolet?visible and photoluminescence) study of these layered silica materials shows that, regardless of the Si/Zn ratio, Zn atoms are organized in well-dispersed, uniform ZnO nanodomains (about 1.2?nm) partially embedded within the silica shee…

A dinuclear rhodium(III) complex with the N,N′-ethylenebis(salicylideneiminato) (salen) ligand in a bridging bis-bidentate mode of coordination. Crystal structure of [{Rh(η2-(C6H4)PPh2)(η2-P(o-ClC6H4)Ph2)}2(salen)](SbF6)2

In this communication we describe the synthesis and crystal structure of the complex [{Rh(η 2 -(C 6 H 4 )PPh 2 )(η 2 -P(o-ClC 6 H 4 )Ph 2 )} 2 (salen)]-(SbF 6 ) 2 , showing the bridging configuration of the salen ligand

Simultaneous substitution of bridging acetate groups and reversible RhC bond cleavage in [Rh2(O2CCH3)3-{(C6H4)PPh2}(HO2CCH3)2] in the presence of CF3CO2H. Crystal structure of [Rh2(O2CCF3)3-{(C6H4)PPh2}(HO2CCF3)2]

Abstract The reaction of the monometallated compound [Rh2(O2CCH3)3 {(C6H4)PPh2}(HO2CCH3)2] (1) with CF3CO2H at room temperature yields [Rh2(O2CCF3)3{(C6H4)PPh2}(HO2CCF3)2] (3) as the only isolable product. Compound 3 has been characterized by X-ray methods. 3 crystallizes in the space group P21 / n. It contains three trifluoroacetate groups bridging a Rh4+2 unit with a RhRh bond distance of 2.438(1) Ă; the fourth bridging ligand is a triphenylphosphine metallated at one of the ortho positions. Two molecules of trifluoroacetic acid occupy the axial coordination positions. In addition to the substitution of acetate groups, reversible electrophilic RhC bond activation is observed.

Generalised syntheses of ordered mesoporous oxides: the atrane route

Abstract A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant–inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructu…

Manganese(II) complexes of scorpiand-like azamacrocycles as MnSOD mimics.

Mn(II) complexes of scorpiand-type azamacrocycles constituted by a tretrazapyridinophane core appended with an ethylamino tail including 2- or 4-quinoline functionalities show very appealing in vitro SOD activity. The observed behaviour is related to structural and electrochemical parameters.

Imidazolate bridged Cu(II)-Cu(II) and Cu(II)-Zn(II) complexes of a terpyridinophane azamacrocycle: a solution and solid state study.

The dinuclear Cu2+ and Zn2+ as well as the mixed Cu2+-Zn2+ complexes of a 5,5''-pentaazaterpyridinophane ligand (L) are able to incorporate imidazolate (Im-) as a bridging ligand. The crystal structure of [Cu(2)L(Im)(Br)(H2O)](CF(3)SO(3))(2).3H2O (1) shows one copper coordinated by the three pyridine nitrogens of the terpyridine unit, one nitrogen of the imidazolate bridge (Im-) and one bromide anion occupying the axial position of a distorted square pyramid. The second copper atom is coordinated by the remaining imidazolate nitrogen, the three secondary nitrogens at the centre of the polyamine bridge and one water molecule that occupies the axial position. Magnetic measurements have been p…

Mesosynthesis of ZnO-SiO(2) porous nanocomposites with low-defect ZnO nanometric domains.

Silica-based ZnO-MCM-41 mesoporous nanocomposites with high Zn content (5≤Si/Zn≤50) have been synthesized by a one-pot surfactant-assisted procedure from aqueous solution using a cationic surfactant (CTMABr = cetyltrimethylammonium bromide) as structure-directing agent, and starting from molecular atrane complexes as inorganic hydrolytic precursors. This preparative technique allows optimization of the dispersion of the ZnO nanodomains in the silica walls. The mesoporous nature of the final materials is confirmed by x-ray diffraction (XRD), transmission electron microscopy (TEM) and N(2) adsorption-desorption isotherms. The ZnO-MCM-41 materials show unimodal pore size distributions without …

Synthesis and Characterization of SiC/MC/C Ceramics (M = Ti, Zr, Hf) Starting from Totally Non-oxidic Precursors

The reaction of poly(dimethylsilane) (PDMS) and poly(dimethylcarbosilane) (PCS) with bis(cyclopentadienyl)M dichloride Cp2MCl2 (M ) Ti, Zr, Hf) complexes has been used as a new route to obtain ceramic materials based on SiC-containing M. The reaction is completed at a relatively low temperature, 900 °C, yielding the corresponding amorphous SiC/MC ceramics which have been characterized by means of 29 Si MAS NMR. These amorphous materials have been treated at higher temperatures, 1350 °C, under a purified argon atmosphere, yielding partially crystallized products which have been studied by X-ray powder diffraction and 29 Si MAS NMR. The effect of the composition of the mixture of precursors is

Hydrogen-bond-mediated self-assembly of 26-membered diaza tetraester crowns of 3,5-disubstituted 1 h -pyrazole. Dimerization study in the solid state and in CDCl3 solution

By using an improved synthetic method reported earlier, the cyclic stannoxanes obtained from RN-diethanolamine (R = Me, Bu) and dibutyltin oxide have been reacted with 1H-pyrazole-3,5-dicarbonyl dichloride to afford 26-membered diaza tetraester crowns (1, R = Me; 3, R = Bu) and 39-membered triaza hexaester crowns (2, R = Me; 4, R = Bu). The new structures were identified from their analytical and spectroscopic (1H and 13C NMR, FAB-MS, and/or ESI-MS) data. Both diaza tetraester crowns (1 and 3), containing two 1H-pyrazole units, self-assemble into dimeric species through the formation of four hydrogen bonds involving the two NH pyrazole groups and the two tertiary amine groups of both crowns…

Low-Cost Synthesis of Bimodal Mesoporous Silica-Based Materials by Pseudomorphic Transformation.

Nanoparticulate bimodal porous silica-based materials have been prepared through a surfactant-assisted procedure by using a simple template and starting from inexpensive sodium silicate as silicon source. Different procedural variables, such as pH or the nature and concentration of the surfactant, have been explored to optimize the preparative protocol, which allows, in turn, improved understanding of the formation process. The final bulk materials (called UVM-10 or M-UVM-10) are formed by pseudomorphic transformation of fresh silica-based xerogels under mild basic conditions. The UVM-10 architecture is constructed from small mesoporous nanoparticles, the aggregation of which generates a di…

CCDC 934155: Experimental Crystal Structure Determination

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CCDC 1423684: Experimental Crystal Structure Determination

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