Inorganic Organic Hybrid Framework Research Articles

New Family of Lanthanide-Based Inorganic–Organic Hybrid Frameworks: Ln2(OH)4[O3S(CH2)nSO3]·2H2O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4) and Their Derivatives

We report the synthesis and structure characterization of a new family of lanthanide-based inorganic-organic hybrid frameworks, Ln(2)(OH)(4)[O(3)S(CH(2))(n)SO(3)]·2H(2)O (Ln = La, Ce, Pr, Nd, Sm; n = 3, 4), and their oxide derivatives. Highly crystallized samples were synthesized by homogeneous precipitation of Ln(3+) ions from a solution containing α,ω-organodisulfonate salts promoted by slow hydrolysis of hexamethylenetetramine. The crystal structure solved from powder X-ray diffraction data revealed that this material comprises two-dimensional cationic lanthanide hydroxide {[Ln(OH)(2)(H(2)O)](+)}(∞) layers, which are cross-linked by α,ω-organodisulfonate ligands into a three-dimensional pillared framework. This hybrid framework can be regarded as a derivative of UCl(3)-type Ln(OH)(3) involving penetration of organic chains into two {LnO(9)} polyhedra. Substitutional modification of the lanthanide coordination promotes a 2D arrangement of the {LnO(9)} polyhedra. A new hybrid oxide, Ln(2)O(2)[O(3)S(CH(2))(n)SO(3)], which is supposed to consist of alternating {[Ln(2)O(2)](2+)}(∞) layers and α,ω-organodisulfonate ligands, can be derived from the hydroxide form upon dehydration/dehydroxylation. These hybrid frameworks provide new opportunities to engineer the interlayer chemistry of layered structures and achieve advanced functionalities coupled with the advantages of lanthanide elements.

Preparation, characterization and electrochemical investigation of a new inorganic–organic hybrid material based on Keggin-type polyoxometalate and organic imidazole cation

A new soluble inorganic–organic hybrid based on polyoxotungstate, [Himi]4[SiW12O40].H2O 1 (imi = Imidazole), has been successfully synthesized and characterized by using elemental analysis, infrared spectrum, 1H NMR technique and single-crystal X-ray diffraction. X-ray crystallography reveals that 1 displays an organic–inorganic hybrid frameworks constructed by [SiW12O40]4−α-Keggin-type polyoxoanion and four {(Himi)}+ monocationic hydrogen-bonded fragments. Redox activities for the tungsten centers have been observed using cyclic voltammetry. It was found that 1 presents good electrocatalytic activities for the reduction of NO2− rather than H4SiW12O40 heteropolyacid.

Poly[bis{μ2-4-[3,5-bis(pyridin-4-yl)phenyl]pyridine}nona-μ2-oxido-tetraoxidocopper(II)tetramolybdenum(VI)

The title compound, [CuMo(4)O(13)(C(21)H(15)N(3))(2)](n), was synthesized by the reaction of ammonium molybdate, copper acetate and 4-[3,5-bis(pyridin-4-yl)phenyl]pyridine (DPPP) in an aqueous medium under hydrothermal conditions. The two unique molybdenum centers and the copper center adopt MoO(4) tetrahedral, MoO(5)N octahedral and CuO(4)N(2) octahedral geometries, respectively. These polyhedra are connected to each other through corner-sharing to form a two-dimensional Cu-Mo-O layer, which is further linked by the DPPP ligands to form the three-dimensional inorganic-organic hybrid framework.

New Multifunctional Porous Materials Based on Inorganic–Organic Hybrid Single‐Walled Carbon Nanotubes: Gas Storage and High‐Sensitive Detection of Pesticides

Single-walled carbon nanotubes (SWNTs) that are covalently functionalized with benzoic acid (SWNT-PhCOOH) can be integrated with transition-metal ions to form 3D porous inorganic-organic hybrid frameworks (SWNT-Zn). In particular, N(2)-adsorption analysis shows that the BET surface area increases notably from 645.3 to 1209.9 m(2) g(-1) for SWNTs and SWNT-Zn, respectively. This remarkable enhancement in the surface area of SWNT-Zn is presumably due to the microporous motifs from benzoates coordinated to intercalated zinc ions between the functionalized SWNTs; this assignment was also corroborated by NLDFT pore-size distributions. In addition, the excess-H(2)-uptake maximum of SWNT-Zn reaches about 3.1 wt. % (12 bar, 77 K), which is almost three times that of the original SWNTs (1.2 wt. % at 12 bar, 77 K). Owing to its inherent conductivity and pore structure, as well as good dispersibility, SWNT-Zn is an effective candidate as a sensitive electrochemical stripping voltammetric sensor for organophosphate pesticides (OPs): By using solid-phase extraction (SPE) with SWNT-Zn-modified glassy carbon electrode, the detection limit of methyl parathion (MP) is 2.3 ng mL(-1).

A Series of Ca(II) or Ba(II) Inorganic–Organic Hybrid Frameworks Based on Aromatic Polycarboxylate Ligands with the Inorganic M–O–M (M = Ca, Ba) Connectivity from 1D to 3D

Solvothermal reactions of Ca(NO3)2 or Ba(NO3)2 with aromatic carboxylate ligands afforded four new inorganic–organic hybrid frameworks, [Ca(PBDC)(H2O)3]n (1), [Ca(OBDC)(H2O)]n (2), [Ba5(OBDC)4(H2O)2(NO3)2]n (3), and [Ba3(BTC)2(H2O)4]n (4) (H2PBDC = terephthalic acid, H2OBDC = phthalic acid, H3BTC = 1,3,5-benzenetricarboxylic acid). These compounds have been fully characterized by single crystal X-ray diffraction, powder X-ray diffraction, satisfactory elemental analysis, IR spectra, and TG analysis. X-ray analysis shows that compound 1 features a one-dimensional chain (1D) structure with the I1O0 connectivity, both compound 2 and compound 3 feature a two-dimensional (2D) layer structure with the I1O1 connectivity, I2O0 connectivity, respectively, compound 4 features a three-dimensional (3D) framework with a rare I3O0 connectivity. Thermal stabilities and luminescent properties of compounds 1–4 and NLO property of compound 4 have also been investigated.

A new luminescent Cu(I) complex stabilized by Cu⋅⋅⋅Cu interactions

Abstract A novel luminescent Cu(I) compound, [Cu(HtrzS)]n (1 HtrzSH=1H-1,2,4-triazole-3-thiol), was hydrothermally synthesized, which features a two-dimensional (2D) inorganic–organic hybrid framework containing a inorganic [CuS]n layer. Further, this 2D framework is connected by the intermolecular hydrogen bonds into a three-dimensional (3D) supramolecular framework. Optical diffuse reflectance study reveals an optical band gap of 3.44 eV, making it a wide band gap semiconductor. Moreover, this compound exhibits strong photoluminescence at room temperature. The densities of states (DOS) calculations reveal that luminescence emission bands of the compound originate from the ligand-to-metal charge transfer.

Adsorption and separation of methane/hydrogen in octaphenylsilsesquioxane based covalently-linked organic-inorganic hybrid framework

The adsorption and separation of CH4/H2 in two covalently-linked organic-inorganic hybrid frameworks polyoctaphenylsilsesquioxane (JUC-Z1) were computationally studied using the Grand Canonical Monte Carlo (GCMC) simulations. The results show that JUC-Z1 with Linde type A (LTA) and polycubane (zeolite code ACO) net topologies can adsorb up to 20.32, 18.57 mmol/g of CH4 and 19.04, 17.89 mmol/g of H2 at 298 K and 10 MPa, respectively. For the adsorption of binary mixture, the selectivity of CH4 over H2 in LTA-JUC-Z1 decrease gradually with the increase of the pressure or the CH4 mole fraction of the mixture. As to ACO-JUC-Z1, the selectivity first increases at low pressure or CH4 mole fraction, and then begins to decrease with the further increase of the corresponding amount. Anyhow, the two materials both exhibit excellent adsorption and separation capacities of CH4/H2.

Nanocrystalline hybrid inorganic–organic one-dimensional chain systems tailored with 2- and 3-phenyl ring monocarboxylic acids

Two novel nanosized hybrid inorganic–organic frameworks, VO(C14H9COO)2, and VO(C10H7COO)2 have been solvothermally synthesized and their structures elucidated using a combination of powder XRD and DFT geometry optimization. They contain one-dimensional chains of corner-sharing tetrahedra in the case of VO(C10H7COO)2, and corner-sharing octahedra for VO(C14H9COO)2 oriented along orthorhombic/monoclinic c-axis, respectively. While VO(C14H9COO)2 exhibits bidentate bridging binding of organic moiety to the metal center, VO(C10H7COO)2 shows a monodentate mode as evidenced from DFT and infrared spectroscopy. Both hybrids exhibit fiber-like morphology, consisting of smaller individual single crystals aligned in parallel to the growth direction along the c-axis. They are thermally stable up to 350 °C having even more stable impurities containing vanadium in its highest oxidation state. The magnetic properties have also been investigated and indicate antiferromagnetic ordering along the chains characterized by rather low spin exchange parameters.

Synthesis, crystal structure and properties of a novel framework aluminium diphosphonate

We report here the hydrothermal synthesis, crystal structure and properties of the hybrid inorganic–organic framework material Al2[O3PC6H4PO3](H2O)2F2·2H2O which is the seventh member of the group 13 metal diphosphonate framework series of formula M(III)2[O3PRPO3](H2O)2F2. The structure is formed from linear chains of corner-sharing AlO4F2 octahedra in which the two fluorine atoms are present in a trans configuration. The diphosphonate groups link the chains together through Al–O–P–O–Al bridges and through the phenylene groups to form a three-dimensional framework structure containing a one-dimensional channel system containing eight non-framework water molecules per unit cell. The framework structure remains crystalline with respect to the loss of the non-framework water molecules but removal of the framework water molecules results in a rapid loss of framework stability and crystallinity. The work demonstrates the potential to design the structure and void volume of a hybrid framework material through directed formation of the extended two-dimensional inorganic component and the packing of the organic component within the interlayer region.

Synthesis, structure and characterizations of a novel 3D coordination polymer constructed from rare castellated inorganic chains

Self-assembly of CdCl 2 and 1,2,4-triazole under hydrothermal condition yields a novel three-dimensional coordination polymer, namely {[Cd 8 Cl 4 (Trz) 12 (H 2 O)]·2H 2 O} n ( 1 ) (Trz = 1,2,4-triazole). Single-crystal X-ray diffraction reveals that four of the five independent Cd centers are linked by two μ 2 -Cl and two μ 3 -Cl atoms to form novel heptanuclear [Cd 7 Cl 4 ] clusters, which are connected by the bridging water molecules to generate an unprecedented 1D castellated inorganic chain. Furthermore, the fifth unique Cd center and the castellated Cd–Cl–O chain are joint to each other via six different μ 3 -Trz ligands to give a 3D organic–inorganic hybrid framework of 1 . A novel 3D hybrid coordination polymer was obtained via the self-assembly of CdCl 2 and 1,2,4-triazole under hydrothermal condition, which is constructed from unprecedented 1D castellated Cd–Cl–O inorganic chains and μ 3 -triazole ligands. ► 1D castellated inorganic chain based on heptanuclear [Cd 7 Cl 4 ] clusters. ► 3D organic–inorganic hybrid framework with rod-packing topology. ► Strong blue photoluminescence attributed to LMCT.

Magnetic and Mechanical Anisotropy in a Manganese 2-Methylsuccinate Framework Structure

Hybrid inorganic-organic framework materials exhibit unique properties that can be advantageously tuned through choice of the inorganic and organic components and by control of the crystal structure. We present a new hydrothermally prepared 3D hybrid framework, [Mn(2-methylsuccinate)](n) (1), comprising alternating 2D manganese oxide sheets and isolated MnO(6) octahedra, pillared via syn, anti-syn carboxylates. Powder magnetic characterization shows that the compound is a homospin Mn(II) ferrimagnet below 2.4 K. The easy-axis is revealed by single-crystal magnetic susceptibility studies and a magnetic structure is proposed. Anisotropic elastic moduli and hardness, observed through nanoindentation on differing crystal facets, were correlated with specific structural features. Such measurements of anisotropy are not commonly undertaken, yet allow for a more comprehensive understanding of structure-property relationships.

Poly[di-μ2-chlorido-tri-μ2-terephthalato-tetralead(II)

The title compound, [Pb4(C8H4O4)3Cl2]n, consists of a three-dimensional inorganic–organic hybrid framework. The asymmetric unit contains two Pb2+ cations, one Cl− anion and one and a half terephthalate anions, the latter being completed by inversion symmetry. The two Pb2+ cations are each surrounded by five O atoms and one Cl atom in the form of irregular polyhedra. The cations are linked by μ2-O and μ2-Cl atoms into binuclear units, which are further extended through Pb—O inter­actions into an undulated inorganic layer parallel to (001). These layers are connected along [001] by the terephthalate groups into a three-dimensional framework.

ChemInform Abstract: Mechanical Properties of Hybrid Inorganic—Organic Framework Materials: Establishing Fundamental Structure—Property Relationships

AbstractReview: 137 refs.

A Vanadium (VO2+) Metal–Organic Framework: Selective Vapor Adsorption, Magnetic Properties, and Use as a Precursor for a Polyoxovanadate

The reaction of VOSO(4) with 2-carboxyethylphosphonic acid (H(2)-CEP) in presence of piperazine (PIP) produces a 3D inorganic-organic hybrid framework, {(H(2)PIP)(0.5)[VO(CEP)]·H(2)O} (1) with bidirectional channels occupied by the H(2)PIP cations and H(2)O molecules. The PO(3)(2-) unit of CEP connects three V(IV) centers to generate a 1D ladder, which is further linked to four such ladders by the CEP linkers to form a 3D hybrid framework. The dehydrated framework, {(H(2)PIP)(0.5)[VO(CEP)]} (1') shows selective and gated adsorption behavior with H(2)O but not with methanol and ethanol. Very interestingly, when 1 is treated with an aqueous solution of LiNO(3)/NaNO(3), the framework breaks down and results in a new polyoxovanadate (POV) cluster, [H(5)(H(2)PIP)(3)][V(V)(12)V(IV)(2)O(38)(PO(4))]·8H(2)O (2) at pH ≈ 2.1. The cluster has been characterized by single-crystal X-ray diffraction, (31)P NMR, EPR, and magnetic studies. The temperature-dependent magnetic susceptibility measurement suggests antiferromagnetic ordering in 1 with T(N) ≈ 3.8 K.

The construction of a new POMs-based inorganic–organic hybrid framework involving in-situ ligand conversion from 1,3-bis(4-pyridyl)propane to isonicotinic acid

A new inorganic–organic hybrid complex, Na 2[{Ag 10(NC 5H 4COO) 8(H 2O) 6}(SiW 12O 40)] ( 1), has been successfully synthesized from [SiW 12O 40] 4− anions, Ag + ions and 1,3-bis(4-pyridyl)propane under hydrothermal conditions and characterized by elemental analyses, IR spectroscopy, TG analyses, and single-crystal X-ray diffraction. In complex 1, each [SiW 12O 40] 4− anion connects with six Ag atoms and in turn each Ag atom links to three [SiW 12O 40] 4− anions, leading to a (6, 3) layer. Such (6, 3) layers are arranged in parallel and further linked by [Ag(H 2O)(NC 5H 4COOH) 2] − fragments to generate a 3D framework. The most striking feature in this work is that 1,3-bis(4-pyridyl)propane converses to isonicotinic acid in the synthetic reaction of 1, which may be induced by the combined function of Ag + ion and polyoxometalate.

Two organic–inorganic hybrid frameworks with unusual inorganic and organic connectivity

Two µ-Cl− bridged Cd(II) organic–inorganic hybrid frameworks have been constructed with unusual I1O3 and I2O2 connectivity, respectively.

Mechanical properties of hybrid inorganic–organic framework materials: establishing fundamental structure–property relationships

The mechanical properties of hybrid framework materials, including both nanoporous metal-organic frameworks (MOFs) and dense inorganic-organic frameworks, are discussed in this critical review. Although there are relatively few studies of this kind in the literature, major recent advances in this area are beginning to shed light on the fundamental structure-mechanical property relationships. Indeed research into the mechanical behavior of this important new class of solid-state materials is central to the design and optimal performance of a multitude of technological applications envisaged. In this review, we examine the elasticity of hybrid frameworks by considering their Young's modulus, Poisson's ratio, bulk modulus and shear modulus. This is followed by discussions of their hardness, plasticity, yield strength and fracture behavior. Our focus is on both experimental and computational approaches. Experimental work on single crystals and amorphized monoliths involved primarily the application of nanoindentation and atomic force microscopy to determine the elastic moduli and hardness properties. The compressibility and bulk moduli of single crystals and polycrystalline powders were studied by high-pressure X-ray crystallography in the diamond anvil cell, while in one instance spectroscopic ellipsometry has also been used to estimate the elastic moduli of MOF nanoparticles and deposited films. Theoretical studies, on the other hand, encompassed the application of first principles density-functional calculations and finite-temperature molecular dynamics simulations. Finally, by virtue of the diverse mechanical properties achievable in hybrid framework materials, we propose that a new domain be established in the materials selection map to define this emerging class of materials (137 references).

A covalently-linked microporous organic-inorganic hybrid framework containing polyhedral oligomeric silsesquioxane moieties

By a Yamamoto-type of Ullmann cross-coupling reaction, a well-defined covalently-linked microporous organic-inorganic hybrid framework polyoctaphenylsilsesquioxane (JUC-Z1) was effectively prepared from the nano building block p-iodio-octaphenylsilsesquioxane (I8OPS) with a yield of ca. 100%. The structure of JUC-Z1 was characterized by (13)C CP/MAS NMR and (29)Si MAS NMR experiments. Fourier transform infrared spectroscopy (FTIR) was performed to confirm the presence of functions in the framework. The results showed that inorganic silsesquioxane cubes were linearly covalently-linked by biphenyls, offering a highly cross-coupling framework. The powder X-ray diffraction (PXRD) pattern and transmission electron microscope (TEM) image show that JUC-Z1 is spherical with uniform micropores. N(2) adsorption results suggest that the hybrid framework has a narrow pore size distribution from 11.8 to 20.0 Å, with a BET surface area of 283 m(2)g(-1) and a pore volume of 0.226 cm(3)g(-1). A thermogravimetric (TG) analysis indicates the thermal stability of JUC-Z1 up to 397 °C in air. Moreover, a liquid sorption experiment reveals the favorable sorption of benzene and water.

Hybrid Zeolitic Imidazolate Frameworks with Catalytically Active TO4 Building Blocks

Crystalline porous materials with diverse chemical compositions (e.g., inorganic porous materials, inorganic–organic hybrid frameworks, and covalent organic frameworks) and framework topologies have been intensively studied in the past 60 years. They have wide applications in fields such as heterogeneous catalysis, gas storage, and separation. Moreover, some currently emerging areas related to health, energy use, and environmental conservation and remediation are still looking for the development of new porous materials. Zeolites are among the most well known porous materials because of their typical 4-connected open frameworks with TO4 (T= Si , Al, or P etc.) building blocks and outstanding catalytic or gas separation properties. Recently, the search for new zeolite-like structures was extended to metal–organic frameworks (MOFs), and these explorations in part produced a variety of zeolitic imidazolate frameworks (ZIFs) in which the tetrahedrally coordinated divalent cations (M=Zn or Co) are connected by the uninegative imidazolate ligands (im ). The rich chemistry associated with the organic imidazolate building blocks in ZIFs leads to some exceptional properties, such as large surface area and high gas uptake capacities. A question that emerges is: “Are there material with properties intermediate of those of zeolites and ZIFs?”. It is true that there is a hybrid state that remains unknown to date. In this work, we were seeking to integrate compositional and structural features of zeolites and ZIFs by combining TO4 tetrahedra with zinc–imidazolate units. Such a combination is trusted to bear both merits of zeolites and ZIFs, for example, possession of catalytic active TO4 sits of zeolites and high porosity of ZIFs. Herein, we report this kind of hybrid zeolitic imidazolate framework [denoted HZIFs; general formula: M4(im)6TO4] with catalytically active TO4 (T=Mo 6+ or W) building blocks and high thermal stability (up to 550 8C), which presents a new class of porous materials filling the gap between zeolites and ZIFs. The HZIFs reported herein are constructed from two kinds of tetrahedral building blocks and contain two kinds of connectivity, and combine structural features of both zeolites and ZIFs (Scheme 1). The TO4 units used in HZIFs are not traditional SiO4 or AlO4 units in aluminosilicate zeolites, but

Synthesis and Photocatalytic Performance of Hierarchical Porous Titanium Phosphonate Hybrid Materials

A hierarchical meso-/macroporous titanium phosphonate (TPPH) hybrid material was prepared via a simple surfactant-assisted process with the use of the precursor tetrabutyl titanate and 1-hydroxy ethylidene-1,1-diphosphonic acid. The prepared hybrid TPPH presented amorphous phase, exhibiting a hierarchical macroporous structure composed of mesopores with a pore size of 2.0 nm. The BET surface area is 256 m2/g. The hydroxyethylidene-bridged organophosphonate groups were homogeneously incorporated in the network of the hierarchical porous solid, as revealed by FT-IR, MAS NMR, XPS, and TGA measurements. The optical properties and photocatalytic activity of the hierarchical TPPH material were investigated in comparison with those of hierarchical porous titanium phosphate and pure mesoporous titania materials, showing superiority of the inorganic-organic hybrid framework, suggesting promising photocatalysts for wastewater cleanup.