Hybrid Solids Research Articles

Synthesis and Characterization of [Mo3S4(NDABu)(HNDABu)2]3– and [Mo3S4(HNDAPr)3]2– Anions as Building Blocks for Organic–Inorganic Hybrid Solids

AbstractThe polymetallic cation [Mo3S4(H2O)9]4+ was used as an inorganic precursor to generate new hybrid organic–inorganic chalcogenide clusters. Three organic compounds with flexible and hanging arms were synthesized and investigated as ligands for coordination complexes with the rigid and electroactive inorganic {Mo3S4} unit. Interestingly, the {Mo3S4} core formed hybrid structures with the flexible H3NDABu [N‐(3‐carboxypropyl)iminodiacetic acid] and H3NDAPr [N‐(2‐carboxyethyl)iminodiacetic acid] ligands, which were characterized by X‐ray crystallography. Surprisingly, no crystals were isolated, when the more rigid H3NDABn [N‐(4‐methoxycarbonylbenzyl)iminodiacetic acid] ligand was used. The two coordination complexes [Mo3S4(NDABu)(HNDABu)2]3– and [Mo3S4(HNDAPr)3]2– were characterized by X‐ray diffraction (XRD), IR spectroscopy, thermal gravimetric analysis (TGA), 1H NMR spectroscopy, elemental analysis, and electrochemistry. The organic ligands H3NDABu, H3NDAPr, and H3NDABn were characterized by XRD, IR, HR mass, and 13C and 1H NMR spectroscopy. [Mo3S4(NDABu)(HNDABu)2]3– and [Mo3S4(HNDAPr)3]2– constitute promising preformed building blocks to generate new organic–inorganic hybrid molecular or extended materials.

Swelling Hybrid Solids

AbstractInorganic solids are usually rigid. Professor Hoppe, all over the years, provided a tremendous number of beautiful examples of their structural organization in oxides and fluorides.1 His immense creativity enriched a lot this part of chemistry, and attracted many colleagues – including myself – toward solid state chemistry. A common idea, associated with the usual definition of solids, was to consider crystallized solids are rigid edifices, within which the only degrees of freedom were the thermal vibration of the atoms forming the compound and the movement of atoms during a displacive structural transition. This implied small displacements of the atoms (0.1 Å < d < 1 Å).In 2002, simultaneously with my friend Susumu Kitagawa from Kyoto university,2–5 we discovered a new behavior of the crystallized solid matter: the unusually large flexibility of crystalline solids (movements of > 5–10 Å), keeping the same topology in the absence of any amorphous intermediate. Knowing your continuous curiosity toward new events in solid state chemistry, I decided to dedicate this tribute to this strange phenomenon, primitively a laboratory curiosity but which became during these last ten years a specific topic attracting chemists, physicists, and computer scientists for the academic point of view, but also companies for the applications this behavior allows. This paper will focus exclusively on the flexibility of three‐dimensional solids.

Syntheses and structure characterization of four inorganic–organic hybrid solids based on N-containing aromatic Brønsted bases and chlorometallates

Four organic–inorganic hybrid complexes ([(HL1)2SnCl6] · 2H2O (1) (L1 = 2-methylquinoline), [(HL2)2(CdCl4)] · 2H2O (2) (L2 = 5,7-dimethyl-1,8-naphthyridine-2-amine), [(H2L2)2SnCl6] · 2(Cl) (3), and [(H2L3)SnCl6] · 2H2O (4) (L3 = 3,6-bis(imidazol-1-yl)pyridazine)) derived from N-containing aromatic Brønsted bases and metal(II) chloride dihydrate (tin(II) chloride dihydrate and cadmium(II) chloride dihydrate) were prepared and characterized by IR, X-ray structure analysis, elemental analysis, and TG analysis. The aromatic rings of the cations in all of the compounds are essentially planar. X-ray diffraction analysis revealed that 2–4 have 3-D network structures built from hydrogen bonds between the cations and chlorometallates. Water molecules also play important roles in structure extension in 1, 2, and 4. The arrangements of the anions and cations in their solid state are dominated by shape, size, and symmetry of the cations and the different structures of the chlorometallates as well as by hydrogen-bond interactions.

Delivery Modulation in Silica Mesoporous Supports via Alkyl Chain Pore Outlet Decoration

This article focuses on the study of the release rate in a family of modified silica mesoporous supports. A collection of solids containing ethyl, butyl, hexyl, octyl, decyl, octadecyl, docosyl, and triacontyl groups anchored on the pore outlets of mesoporous MCM-41 has been prepared and characterized. Controlled release from pore voids has been studied through the delivery of the dye complex tris(2,2'-bipyridyl)ruthenium(II). Delivery rates were found to be dependent on the alkyl chain length anchored on the pore outlets of the mesoporous scaffolding. Moreover, release rates follow a Higuchi diffusion model, and Higuchi constants for the different hybrid solids have been calculated. A decrease of the Higuchi constants was observed as the alkyl chain used to tune the release profile is longer, confirming the effect that the different alkyl chains anchored into the pore mouths exerted on the delivery of the cargo. Furthermore, to better understand the relation between pore outlets decoration and release rate, studies using molecular dynamics simulations employing force-field methods have been carried out. A good agreement between the calculations and the experimental observations was observed.

New types of hybrid solids of tetravanadate polyanions and cucurbituril

Three inorganic-organic hybrid solids based on tetravanadate polyanions, {V(4)O(12)}(4-) and cucurbituril, Me(10)Q[5] and Q[5], namely (NH(4))(4)[(V(4)O(12))·(Me(10)Q[5]@0.5H(2)O)(2)]·∼13H(2)O (1), Li(4)(H(2)O)(5)[(V(4)O(12))·(Me(10)Q[5]@H(2)O)(2)]·∼20H(2)O (2), and Na(4)(H(2)O)(2)[(V(4)O(12))·(Q[5])(2)]·∼15H(2)O (3), have been synthesized under hydrothermal conditions. In the structure of compound 1, two {Me(10)Q[5]@0.5H(2)O} moieties connect to one {V(4)O(12)}(4-) cluster through an NH(4)(+) counter-cation to form a trimer unit, which further forms a three-dimensional (3D) supramolecular architecture via extensive hydrogen bonds (H-bonds). Compound 2 contains a one-dimensional (1D) covalently bonded chain structure built by alternate {Me(10)Q[5]@H(2)O} moieties and {Li(2)O(4)(H(2)O)(3)}(2+) dimer units. The anionic {V(4)O(12)}(4-) units bond to every another {Li(2)O(4)(H(2)O)(3)}(2+) dimer unit sitting on the chain through multi-uncoordinated water molecules via H-bonds. Compound 3 is built from {V(4)O(12)}(4-) clusters, Q[5], and sodium cations into a two-dimensional (2D) covalent wavy structure, showing interesting connection between the building units, which is packed into 2D through plentiful H-bonds. It has been found that the cations dramatically affect the coordination of the tetravanadate polyanion and cucurbituril.

Preparation and Characterization of Two Bismuth(III) Iodide Inorganic/Organic Hybrid Solids

Two new organic/bismuth(III) iodide hybrids have been synthesized by a solution process, and their crystal structures were determined by an x-ray diffraction method. The first one, (EMP)3(Bi2I9) (EMP+ = N-ethyl-4-methyl-pyridinium) (1), crystallizes in the monoclinic system, space group P21/c, with M r = 3838.20, a = 19.945(4), b = 12.636(3), c = 20.327(4) Å, β = 118.82(3)°, V = 4488.4(16) Å3, Z = 2, D c = 2.840 g/cm3, F(000) = 3358, μ(MoKα) = 14.039 mm−1, the final R = 0.0678, and wR = 0.1676 for 7272 observed reflections with I > 2σ(I). The second, [(Phendione)BiI4]·(Phendione-H)·C2H5OH (Phendione = 1,10-phenathroline-5,6-dione) (2), belongs to the monoclinic system, space group C2/c, with M r = 1183.02, a = 37.254(8), b = 8.1776(16), c = 22.318(5) Å, β = 111.38(3)°, V = 6331(2) Å3, Z = 8, D c = 2.842 g/cm3, F(000) = 4296, μ(MoKα) = 9.511 mm−1, the final R = 0.0526, and wR = 0.1050 for 6555 observed reflections with I > 2σ(I). Compound 1 contains halobismuthate dimers, and it is noteworthy that the dimers and its organic countercations connect with each other by C–H···I hydrogen bonds to form a layered structure. Compound 2 is composed of [(Phendione)BiI4]− anions and Phendione-H+ cations, and hydrogen bonds contribute to give a one-dimensional (1-D) chain. The optical absorption spectra of 1 and 2 reveal the appearance of sharp optical gaps of 2.17 and 1.93 eV, respectively.

Synthesis, structures and properties of new hybrid solids containing ruthenium complexes and polyoxometalates

Two new organic–inorganic hybrid solids containing Keggin ions and ruthenium complexes have been synthesized and characterized by FT-IR, UV–vis, luminescence, X-ray, and TG analysis. In KNa[Ru(bpy) 3] 2[H 2W 12O 40]·8H 2O ( 1), the [Ru(bpy) 3] 2+ (bpy=2,2′-bipyridine) complex ions are located in between the infinite one-dimensional double-chains formed by adjacent Keggin anions [H 2W 12O 40] 6− linked through {KO 7} and {NaO 6} polyhedra, while in K 6[Ru(pzc) 3] 2[SiW 12O 40]•12H 2O ( 2), the [Ru(pzc) 3] − (pzc=pyrazine-2-carboxylate) complex anions are confined by layered networks of the [SiW 12O 40] 4− clusters connected by potassium ions. Both compounds exhibit three-dimensional frameworks through noncovalent interactions such as hydrogen bonds and anion⋯π interactions. Additionally, compound 1 shows strong luminescence at 604 nm in solid state at room temperature.

Investigation of Trimetallic Ligand-Pillared Oxyfluorides: Ag2Cu(pzc)2MO x F6−x (M = Mo, Nb, and W)

Three new ligand-pillared hybrid solids, Ag2Cu(pzc)2MO x F6−x (I, M = Mo, x = 2; II, M = W, x = 2; III, M = Nb, x = 1) (pzc = pyrazine-2-carboxylate) were synthesized via hydrothermal reactions at 150 °C, and their structures were determined by single-crystal X-ray diffraction (P21/n (No. 14), Z = 2; a = 7.2302(1), 7.2124(2), 7.2715(2) A; b = 7.9460(1), 7.9270(2), 7.98436(3) A; c = 13.9173(2), 13.8959(4), 13.8226(5) A, for I, II, and III, respectively). All three are isostructural and contain unusual trimetallic (Ag2CuMO x F6−x )2+ layers that consist of [Ag2O2F2] n and [CuMO x F6−x ] n chains that alternate within the layers. Each structure also contains [MO x F6−x ]2− octahedra with fully disordered O/F positions and with an inversion center on the Mn+ sites, i.e., Mo6+, W6+ and Nb5+. Magnetic susceptibility measurements can be fitted to the Curie–Weiss law with a Curie constant consistent with a single non-interacting Cu(II) (S = ½) site per formula unit. Thermogravimetric analyses indicate that these hybrid compounds are stable up to ~280 °C, with each exhibiting a single weight-loss step beginning at ~300 °C that corresponds to the loss of all pyrazine-2-carboxylate ligands and additional O/F atoms via oxidation of the ligand during its removal. UV–Vis diffuse reflectance measurements show that each exhibits an optical bandgap size of ~2.8 eV, and which electronic-structure calculations show arise from excitations between the Cu(II)-based valence orbitals and the M5+/6+-based conduction band orbitals. Three new ligand-pillared hybrid solids, Ag2Cu(pzc)2MO x F6−x (M = Mo, W, Nb) were synthesized and contain unusual trimetallic (Ag2CuMO x F6−x )2+ layers. Each exhibits an optical bandgap size of ~2.8 eV, and which electronic-structure calculations show arise from excitations between the Cu(II)-based valence orbitals and the M5+/6+-based conduction band orbitals.

ChemInform Abstract: Postsynthetic Modification of Metal—Organic Frameworks — A Progress Report

AbstractReview: 73 refs.

Self-assembly of 1D metalloporphyrin array within pseudo-hexagonal channels of polyoxometalates

Self-assembly of the robust Keggin cluster [SiW12O40]4− and metalloporphyrin building blocks [M(TpyPHn)]n+ under hydrothermal conditions gives two new organic–inorganic hybrid solid compounds. The hydrothermal reactions of H4SiO4·12WO3·xH2O, Cu(NO3)2·2.5H2O, meso-tetra(4-pyridyl)porphine (H2TpyP) and H2O at 200°C for 72h yield a solid compound [Cu(TpyPH3)]2[Cu(TpyPH2)][SiW12O40]2·8H2O (1). Using ZnCl2 instead of Cu(NO3)2·2.5H2O in the syntheses leads to the crystallization of a compound [Zn(TpyPH4)(H2O)][SiW12O40]·3H2O (2). Both compounds consist of discrete anionic α-[SiW12O40]4− clusters, cationic metalloporphyrins and crystalline water molecules. Hydrogen bonds, π–π aromatic interactions and CH···π interactions in these two new hybrid solids lead to the formation of 3D framework structures. Pseudo-hexagonal channels are formed by polyoxometalates and are occupied by one-dimensional metalloporphyrin arrays. Both compounds were characterized by single crystal X-ray, UV–Vis, IR spectroscopy and thermogravimetric analysis.

Synthesis of Organic−Inorganic Hybrid Solids with Copper Complex Framework and Their Catalytic Activity for the S-Arylation and the Azide−Alkyne Cycloaddition Reactions

Two different diamines, namely, Troger base and dimethylethylene diamine (DMEDA) functionalized with disilane groups, have been condensed with silica precursors to form mesoporous hybrid organic−inorganic materials. After introduction of copper, the Cu-diamine complexes are produced. These hybrid solids have been fully characterized and are active catalysts for the S-arylation of aryl iodides and bromides with thiophenols and disulfides. Additionally, the hybrids show catalytic activity for the cycloaddition reaction between azides and phenylacetylenes. The reaction conditions determine the recovery and reuse of the solid.

Postsynthetic modification of metal–organic frameworks—a progress report

Metal-organic frameworks (MOFs) are an important class of hybrid inorganic-organic materials. In this tutorial review, a progress report on the postsynthetic modification (PSM) of MOFs is provided. PSM refers to the chemical modification of the MOF lattice in a heterogeneous fashion. This powerful synthetic approach has grown in popularity and resulted in a number of advances in the functionalization and application of MOFs. The use of PSM to develop MOFs with improved gas sorption, catalytic activity, bioactivity, and more robust physical properties is discussed. The results reported to date clearly show that PSM is an important approach for the development and advancement of these hybrid solids.

ChemInform Abstract: Metals@MOFs — Loading MOFs with Metal Nanoparticles for Hybrid Functions

AbstractReview: about 50 refs.

Synthesis and characterization of two novel organic–inorganic hybrid solids from Keggin ions and metal coordination complexes

Two new hybrid compounds, [Co(4,4′-bpy) 2(H 2O) 4][(4,4′-bpyH 2] 2[CoW 12O 40]·8H 2O ( 1) and [Fe(2,2′-bpy) 3] 3[H 2W 12O 40]·6H 2O ( 2), (4,4′-bpy = 4,4′-bipyridine, 2,2′-bpy = 2,2′-bipyridine) have been hydrothermally synthesized. These solids were characterized by elemental analysis, thermogravimetric analysis, UV–Vis spectroscopy and X-ray diffraction. The hydrogen-bonding interactions in 1 lead to the formation of a three dimensional network consisting of [CoW 12O 40] 6− anionic clusters, [Co(4,4′-bpy) 2(H 2O) 4] 2+ cations and lattice water molecules, while the discrete Keggin ion [H 2W 12O 40] 6− in compound 2 is surrounded by 14 [Fe(2,2′-bpy) 3] 2+ complexes through CH⋯O interactions (2.24–2.56 Å).

Experimental and Molecular Simulation Investigation of Enhanced CO2Solubility in Hybrid Adsorbents

Hybrid adsorbents are prepared by confining physical solvents (propylene carbonate, N-methyl-2-pyrrolidone) within the porosity of a solid support (alumina) using both wet and dry impregnation methods. The resulting hybrid solids are analyzed using characterization methods (N(2) adsorption isotherm, TGA) to ensure that a proper confinement of the solvent has been achieved. The hybrid adsorbents are then subsequently assessed for CO(2) capture by performing solubility measurements. An enhanced CO(2) solubility is observed with regard to the ones in the bulk solvent and in the raw solid. In a next step, grand canonical Monte Carlo simulations have been performed on a slit pore model to understand the microscopic mechanisms yielding the apparition of enhanced solubility. The presence of solvent molecules favors the layering of CO(2) within the pore, and the resulting local density profile is then markedly increased compared to one found in the raw adsorbent as more carbon dioxide molecules can be accommodated into the pore volume.

Des nanovecteurs hybrides pour la restitution retard de médicaments antitumoraux et antiviraux

The efficient delivery of drugs in the body requires the use of non-toxic nanocarriers. Most of the existing materials show poor drug loading and/or rapid release of the proportion of the drug that is simply adsorbed (or anchored) at the external surface of the nanocarrier. The new porous hybrid solids, with the ability to tune their structures and porosities are well suited to serve as nanocarriers for delivery and imaging applications. Here we show that specific non-toxic porous iron(III) - based metal - organic frameworks with engineered cores and surfaces, as well as imaging properties, function as superior nanocarriers for efficient controlled delivery of antitumour and retroviral drugs against cancer and AIDS. They also potentially associate therapeutics and diagnostics, and open the way for theranostics, or -personalized patient treatments. double dagger.

Syntheses and structural characterization of inorganic–organic hybrid solids of bis-imidazolium chlorocadmate complexes

Six organic–inorganic complexes derived from bis-imidazole derivatives ([(H2L1)(CdCl3 ⋅ H2O)2] (1), L1 = 1-(3-(1H-benzimidazol-1-yl)propyl)-1H-benzimidazole; [(H2L2)CdCl4] (2), L2 = 1,1′-bis(benzimidazolyl)methane; [(H2L3)CdCl4] (3), L3 = 1-(2-(1H-benzimidazol-1-yl)ethyl)-1H-benzimidazole; [(H2L4)4(CdCl4)4] ⋅ 13H2O (4), L4 = 1,5-bis(1-benzimidazolyl)-3-oxapentane; [(H2L5)CdCl4] (5), L5 = 1-(4-(1H-benzimidazol-1-yl)butyl)-1H-benzimidazole; [(H2L6)(Cd2Cl8)0.5] ⋅ H2O (6), L6 = 3,6-bis(imidazol-1-yl)pyridazine), and cadmium(II) chloride dihydrate were prepared and characterized by IR, X-ray structure analysis, elemental analysis, and TG analysis. The imidazolyl moieties in all six compounds are essentially planar. X-ray diffraction analysis revealed that complexes 1–6 have 3-D network structures built from hydrogen bonds between imidazolium cations, chlorocadmate anions, and water. The arrangements of the anions and cations in their solid state are dominated not only by the size and symmetry of the imidazolium cations, but also by the different structure types of the chlorocadmate anions as well as the hydrogen-bonded interactions existing in the crystal structures. All of the complexes are thermally stable.

Metals@MOFs – Loading MOFs with Metal Nanoparticles for Hybrid Functions

AbstractMetal–organic frameworks (MOFs) as well as porous coordination polymers (PCPs) are porous, organic–inorganic hybrid solids with zeolite‐like structures and properties. Due to their extraordinarily high surface area and well defined pore structure MOFs can be used for the stabilization of metal nanoparticles with adjustable size. The embedded metal nanoparticles are still accessible for other reagents due to the high porosity of the MOF systems. This fact makes “metal@MOF” systems especially interesting for heterogeneous catalysis, gas storage and chemical sensing. This review compiles the cases of metal nanoparticles supported by or embedded into MOFs reported so far and the main aspects and problems associated with these novel nanocomposite systems. The determination of the dispersion and the location of the particles at the MOF support, the control of the loading degree and its effect on the catalytic activity of the system are discussed as well as the partial degradation of the MOF structure upon particle formation. Examples of the introduction of stabilizing groups into the MOF network that direct the loading and can influence the size and shape of the embedded particles are still rare and point into the possible direction of future investigations. Finally, the formation of bimetallic nanoparticles, which are stabilized and supported by a MOF network, will also be reviewed.

ChemInform Abstract: Structures, Properties, and Potential Applications of Ormosils

Ormosils are organic-inorganic hybrid solids in which the organic component may be chemically bonded to a silica matrix. Somewhat similar to inorganic silicate glasses, the structure of the silica network can be modified by the presence of organic groups. The resulting properties of the Ormosils are then governed by the type and concentration of organics used. Examples are presented in which the mechanical, electrical and optical properties of selected Ormosils can be influenced by organic groups. For instance, small amounts of polydimethylsiloxane (PDMS) added to a solution of TEOS will give an Ormosil about ten times harder than the hardest organic polymer. Larger amounts of PDMS (20%) will now yield an Ormosil which is as rubbery as organic rubber. Ormosils in which the organic and inorganic constituents are covalently bound to each other are the focus of this critical review. The potential applications of such Ormosils are discussed.

Real‐time hybrid solid simulation: spectral unification of deformable and rigid materials

AbstractA novel framework is proposed in this paper to simulate hybrid solids with deformable and rigid materials in real‐time. Both types of materials are uniformly integrated into one spectral simulator. Based on the modal warping technique, we employ a new constraint strategy which eliminates the accumulation of approximation errors at the boundary interfaces, thus naturally gluing different materials. We also utilize the GPU to accelerate the run‐time computation when updating the geometry of the hybrid solid—the most expensive step in this framework. This work provides a general‐purpose solution of simulating hybrid objects in real‐time, even for large‐scale models. Copyright © 2010 John Wiley & Sons, Ltd.