Organic Inorganic Hybrid Solids Research Articles

A confinement-regulated (H3C-NH3)+ ion as a smallest dual-wheel rotator showing bisected rotation dynamics.

On the basis of variable-temperature single-crystal X-ray diffraction, rotational energy barrier analysis, variable-temperature/frequency dielectric response, and molecular dynamics simulations, here we report a new crystalline supramolecular rotor (CH3NH3)(18-crown-6)[CuCl3], in which the (H3C-NH3)+ ion functions as a smallest dual-wheel rotator showing bisected rotation dynamics, while the host 18-crown-6 macrocycle behaves as a stator that is not strictly stationary. This study also provides a helpful insight into the dynamics of ubiquitous -CH3/-NH3 groups confined in organic or organic-inorganic hybrid solids.

Impregnation of Synthetic Saponites with Aldehydes: A Green Approach in the Intercalation of Bioactive Principles

Synthetic saponite clay was impregnated with either linear saturated or unsaturated aldehydes through an incipient-wetness deposition approach. To increase the aldehyde loading, saponite was also intercalated with positively charged cetyltrimethylammonium (CTA+) species, aiming to expand the clay gallery and to increase the hydrophobic character of the host solid. A multitechnique, physicochemical investigation was performed on the organic–inorganic hybrid solids. The analyses revealed that the aldehydes are mainly adsorbed on the clay particles’ surface, with a small fraction inside the interlayer space. In CTA+-modified saponites, the concentration of saturated aldehydes was higher than the one observed in the pure clay. These features are quite promising for the development of novel layered solids containing bioactive molecules for ecocompatible and economically sustainable applications, especially in agriculture, for the development of innovative hybrid materials for crop protection.

Indium phosphate oxalates with layered structures: Solvent-free approach, hydrothermal stability, and proton conduction

Two new crystalline indium phosphate oxalates (denoted SCU-23 and SCU-25) were synthesized by a solvent-free approach. The two inorganic-organic hybrid solids have different layered structures intercalated with organic cations. Notably, SCU-25 remains stable in boiling water and shows appealing proton conductive behaviors.

Syntheses and structural characterization of eight inorganic-organic hybrid solids based on N-Brønsted bases and halometallates of Zn, Cu, Sb and Bi

Eight organic-inorganic hybrid salts [(HL1)(SbCl4)] (1) (L1 = N,N-dimethylbenzylamine), [(HL2)2(ZnCl4)] (2) (L2 = 4-chlorobenzylamine), [(HL2)(L2)(CuCl3)(H2O)2] (3), [(HL3)2(Sb2OCl6)] (4) (L3 = quinoline), [(HL4)4(Bi2Cl10)] (5) (L4 = 2-methylquinoline), [(HL5)(SbCl4)] (6) (L5 = 5,7-dimethyl-1,8-naphthyridine-2-amine), [(H2L6)(SbCl5)] (7) (L6 = 3,6-bis(imidazol-1-yl)pyridazine) and [(H2L7)2(CuBr4)2] · 7H2O (8) (L7 = di(2-benzimidazol-1-ylethyl)ether) were prepared and characterized by IR, XRD, EA and TG analysis. XRD analysis told that all of the complexes were 3 D net built from non-covalent bonds from the cations and the halometallates. The aryl rings of the cations in all of the compounds are essentially planar. The H2O also had crucial role in structure extension in 3 and 8. Extensive intermolecular interactions have been used in the self-assembly of diverse motifs, ranging from strong N-H···X (X = Br, Cl), N-H···O, N-H···N, O-H···O, O-H···Br H-bonds to weak CH2···O, CH3-Cl/CH2-Cl/CH-Cl, Cl-Cl, O-Br, CH3-π, CH2-π, Cl-π and π-π associations. The arrangements of the anions and cations in the solid are ruled not only by the size and symmetry of the cations, but also by the non-covalent bonds in the crystal structures.

Solvent-free synthesis of inorganic-organic hybrid solids with chainlike, layered, and open-framework structures

Three inorganic-organic hybrid solids, namely, Cd2(phen)2(H2PO4)(H2PO3)(C2O4) (1), (H2dab)0.5·Co(H2PO3)(C2O4) (2), and Hdbu·In2(HPO3)2(C2O4)1.5 (3), were prepared under solvent-free conditions, where phen = 1,10-phenanthroline, dab = 1,4-diaminobutane, and dbu = 1,8-diazabicyclo[5.4.0]undec-7-ene. These compounds have chainlike, layered, and three-dimensional structures, respectively. Compound 1 shows a weak second harmonic generation response. The temperature dependence of the magnetic susceptibility of compound 2 was also investigated.

Sandwich-type Inorganic–Organic Hybrid Solids of Iso-polyvanadate Clusters and Decamethylcucurbit[5]uril

Three sandwich-type inorganic–organic hybrid solids based on iso-polyvanadate cluster, {V4O12}4–, {H2V6O18}4–, or {H2V10O28}4–, and decamethylcucurbit[5]uril (Me10CB[5]) have been synthesized under hydrothermal conditions. In the structures of (NH4)4[(V4O12)·(Me10CB[5]@0.5H2O)2]·∼15H2O (1) and (NH4)4[(H2V10O28)·(Me10CB[5]@H2O)2]·∼16H2O (3), tetranuclear {V4O12}4– or decanuclear {H2V10O28}4– clusters are sandwiched by (NH4)2@Me10CB[5] closed molecular capsules, through hydrogen-bonding interactions, whereas compound 2, formulated as Li4(H2O)6[(H2V6O18)·(Me10CB[5]@H2O)2]·∼14H2O, is built by hexanuclear {H2V6O18}4– clusters that are covalently sandwiched by Li2@Me10CB[5] half-open molecular capsules in a way similar to thoset of 1 and 3. Compounds 1–3 represent rare examples of sandwich-type polyoxometalate (POM)-based materials in which POM units are inserted at the inner sphere by either hydrogen or covalent bonds. Compound 2 has shown rational photocatalytic activity toward the degradation of methyl orang...

Assembly of two novel inorganic–organic hybrid solids based on 3-(aminomethyl)pyridine ligand

Two new inorganic–organic hybrids, (Hampy)Zn2(PO4) (HPO3) (1) and (ampy)Zn2(HPO3)2 (2), where ampy = 3-(aminomethyl)pyridine, have been solvothermally prepared and structurally characterized. Compound 1 exhibits an unusual two-dimensional layer structure, which possesses a central 4.82 zincophosphate sheet wrapped by infinite zincophosphite chains. Left- and right-handed helical chains participate in the formation of the zincophosphate layer. Compound 2 features a three-dimensional pillared-layer structure, in which two-dimensional ZnII(HPO3) inorganic sheets were cross-linked by ampy ligands. The simultaneous occurrence of zinc-amine helical chains in 2 is unique and, to the best of our knowledge, firstly encountered in phosphite/phosphate hybrid materials. Different coordination modes and roles of the same ampy ligand were observed in the formation of the hybrid structures.

Solvent-free synthesis of new inorganic-organic hybrid solids with finely tuned manganese oxalate structures.

Three manganese phosphate-oxalates have been synthesized under solvent-free conditions. These inorganic-organic hybrid solids are based on a pcu-type topology with nanobelt-like, sql-, and cds-type manganese oxalate skeletons, respectively. The amine molecules play a novel structure-directing role for the formation of different metal-organic skeletons within a specific framework topology.

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.

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.

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.

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).

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.

Two anionic [Cu I6X7] nn− ( X=Br and I) chain-based organic–inorganic hybrid solids with N-substituted benzotriazole ligands

Solvothermal reactions of the flexible ligand 1,6-Bi(benzotriazole)hexane with CuI and KI or CuBr and KBr in ethanol generate two hybrid compounds, namely, {(HETA)[(Cu 6I 7)(ETA) 2]} n ( 1) and {K(Cu 6Br 7)(BBTH)} n ( 2) (ETA= N-ethylbenzotriazole, HETA=protonated N-ethylbenzotriazole, BBTH=1,6-bi(benzotriazole)hexane). In 1, two [Cu 3I 4] vertex missing cubane-like subunits link each other by sharing one I atom to give a [Cu 6I 7] cluster, which further form novel 1D [Cu 6I 7] n n− anionic chain. Two in-situ generated ETA ligands finished the 4-coordinated environments of copper centers and another one discrete protonated ETA ligand keeps the charge neutrality for 1. In complex 2, bowl-shaped [Cu 5Br 4] clusters and rhomboid [Cu 2Br 2] dimers link each other to generate a [Cu 6Br 7] n n− 1D chain. BBTH ligands complete the tetrahedral spheres of Cu(I), and 7-coordinated K atoms further extend the 1D chain motifs to a 2D hybrid layer of 2. The UV–vis diffuse reflectance spectrum and luminescence measurements show that compound 1 and 2 both are potential semiconductor and photoluminescence materials.

Novel compounds based on [Re6Q8(L)6]4− (Q = S, Se, Te; L = CN, OH) and their applications

[Re6Q8L6]4− (Q = S, Se, Te) clusters can serve as promising “building blocks” for the creation of new porous framworks, nanoparticles and mesoporous materials. Since [Re6Q8L6]4−clusters have multi-anchoring sites for transition metals, metal–organic complexes, polymers, and multidentated metal complexes, they could be assembled to form various inorganic or organic–inorganic hybrid solids with new various spatial and chemical functions. Because of the controllable architectures and multi-anchoring sites of clusters together with their photoluminescence, rhenium cluster complexes are promising potential candidates as catalysts, chemical color sensors, magnetic materials, gas storage materials, optoelectronic, diagnostic agents, and gene/drug carriers. A new type of mesoscale material comprising [Re6Q8(CN)6]4− and various divalent transition metals in the presence of a liquid crystal template are obtained in 3D cubic, 2D hexagonal, and lamellar phases. The hexahydroxo complexes [Re6Q8(OH)6]4− (Q = S, Se) with high reactivities and a unique rhenium sulfido–cyanide compound, K8[Re12CS17(CN)6] with a C-centered {Re12} cluster unit were discovered and still many more new rhenium metal cluster complexes at various reaction conditions remain to be explored.

A non-photochemical route for the regioselective preparation of rtct-pyridylcyclobutanes via hydrothermal isomerisation promoted by polymolybdates

A novel approach for the regioselective preparation of rtct-tpcb (tpcb = tetrapyridylcyclobutanes) compounds promoted by polymolybdates under hydrothermal conditions is reported; these isomers are stabilised as counterions in inorganic-organic hybrid solids and are obtained in high to fair yield.

Hydrothermal synthesis and structures of organic–inorganic hybrid solids based on arsenic-vanadate building blocks

Four novel organic–inorganic hybrid arsenic-vanadate complexes, [Cu(phen)][(AsVO4)(VV 3O7)(H2O)] (1), [Cu(en)2]2[As8V14O42(H2O)] · 2.5H2O (2), [M(1,10-phen)3]2[As8V14O42(H2O)0.5] · 0.5H2O (M = Mn, 3, Cd, 4) (1,10-phen = 1,10-phenanthroline) have been hydrothermally synthesized for the first time and characterized by elemental analyses, XPS spectra, EPR spectra, IR spectra, TG analyses and single crystal X-ray diffraction. The structure of compound 1 consists of arsenic vanadate ribbons coordinated by the [Cu(phen)]2+ complex, while compounds 2 to 4 possess a spherical [As8 IIIV14 IVO42]4− cage with H2O molecules encapsulated. The unexpected preparation 1 and the synthesis of compounds 2 to 4 on the basis of same polyoxoanion structures show that the pH value of the reaction plays a crucial role in controlling the basic architectures.