Inorganic Organic Hybrid Framework Research Articles

Acid–Base Bifunctional Periodic Mesoporous Metal Phosphonates for Synergistically and Heterogeneously Catalyzing CO2 Conversion

Integrating multiple functions into one host for improved catalytic performance is challenging and promising for both catalysis and material science. Herein a new acid–base bifunctional periodic mesoporous titanium phosphonate hybrid material is synthesized by a facile one-pot hydrothermal method, using alendronate sodium trihydrate as a coupling molecule. The new material possesses highly periodic mesopores with a large specific surface area of 540 m2 g–1 and pore volume of 0.43 cm3 g–1, favoring the smooth mass transport of reactants and products during the catalytic reaction. It also has an organic–inorganic hybrid framework with homogeneously incorporated phosphonate groups, in which a large number of accessible acidic P–OH and basic −NH2 sites can, respectively, activate aziridine and CO2, synergistically leading to the high conversion (>99%), yield (98%), and regioselectivity (98:2) for the CO2 cycloaddition reaction. The catalytic activity is better than that of the scarcely reported heterogeneous ...

Solvent-free synthesis of new metal phosphites with double-layered, pillared-layered, and framework structures

Three new metal phosphites, formulated as (H3O)2·Mn2(HPO3)3 (1), Co(bpy) (H2O) (HPO3) (2), and H2tmpda·Zn3(HPO3)4 (3), have been synthesized under solvent-free conditions, where bpy = 4,4′-bipyridine, and tmpda = N,N,N′,N′-tetramethyl-1,3-propanediamine. Compound 1 has a double-layered structure with a thickness of 5.68 Å. Compound 2 has an inorganic-organic hybrid framework with cobalt phosphite layers pillared by bpy ligands. Compound 3 has a three-dimensional open-framework structure containing 8-ring channels. The temperature dependence of the magnetic susceptibility of compounds 1 and 2 were also investigated.

ChemInform Abstract: Acentric and Chiral Heterometallic Inorganic‐Organic Hybrid Frameworks Mediated by Alkali or Alkaline Earth Ions: Synthesis and NLO Properties

AbstractReview: 94 refs.

Hydrothermal Synthesis and Characterization of a Novel 1D Zn(II)-Triazole Framework Containing Infinite Zn-O-Zn Connectivity

Using the benzene-based bis-triazole ligand 1,4-di-(1,2,4-triazole-4-yl)benzene(L) and corresponding Zinc(II) salt, under hydrothermal conditions, a novel luminescent 1D Zn(II) coordination polymer, {[Zn2(μ2-O)(μ2-L)]SiF6·3H2O}n (1), has been isolated and characterized by single-crystal X-ray diffraction analysis. The crystal crystallizes in the orthorhombic Cmcm space group, a = 22.867(15) Å, b = 23.751(15) Å, c = 6.778(4) Å, β = 90°, Z = 1. These L ligands adopt the bidentate bridging coordination modes to link neighboring Zn(II) ions forming 1D chain structure. Interestingly, infinite Zn-O-Zn connectivity also can be observed. The result also represents a good example of the construction of these highly dimensional luminescent inorganic-organic hybrid frameworks containing infinite M-O-M linkage using triazole derivative ligands.1

Hydrothermal Synthesis and Characterization of a Novel 1D Luminescent Zn(II) Framework With 1,4-di-(1,2,4-triazole-4-yl) Benzene

Using the benzene-based bis-triazole ligand 1,4-di-(1,2,4-triazole-4-yl)benzene(L) and corresponding zinc(II) salt, under hydrothermal conditions, a novel luminescent 1D Zn(II) coordination polymer, {[Zn(μ2-L)(H2O)4]SiF6·2H2O}n (1) has been isolated and characterized by single-crystal X-ray diffraction, FT-IR, and luminescent analysis. The crystal crystallizes in the Monoclinic C2/c space group, a = 12.997(5) Å, b = 19.376(4) Å, c = 8.080(6) Å, β = 109.379(18)°, Z = 4. These L ligands adopt the bi-dentate bridging coordination modes to link neighboring Zn(II) ions forming 1D chain structure. Solid state luminescent spectrum of 1 also has been investigated indicating the strong emission band centered at 370 nm. The result also represents a good example of the construction of these highly dimensional luminescent inorganic-organic hybrid frameworks.

A series of lanthanide organic–inorganic hybrid frameworks with unusual trinodal topology: Syntheses, structures and magnetic properties

Five isomorphous lanthanide–organic frameworks based on 3-carboxymethoxy phenyl acrylic acid (H2L), [LnL(HCOO)(H2O)]n (Ln=La(1), Ce(2), Pr(3), Nd(4), Y(5)), have been hydrothermally synthesized. X-ray structural analysis reveals that these complexes are rare organic–inorganic hybrid frameworks with unusual (3, 4, 7)-connected (42.6) (44.62) (49.68.84) topology. Moreover, the magnetic properties of 2 and 3 were also investigated and suggested that the thermal depopulation of the crystal-field energy levels of the multiplet, and the antiferromagnetic interactions between Ln3+ ions.

Synthesis, characterization and electrochemical investigation of a new inorganic–organic hybrid compound constructed by Keggin-type polyoxometalate and cyanoguanidine

An inorganic–organic hybrid complex [HDCD]3[PW12O40]·3H2O (1) (DCD = 2-cyanoguanidine) has been synthesized from the reaction of Keggin polyanion and cyanoguanidine (C2N4H4) under mild condition, and characterized by using elemental analysis, infrared spectrum, thermogravimatric analysis and single crystal X-ray diffraction. X-ray crystallography reveals that 1 displays an inorganic–organic hybrid frameworks constructed by [PW12O40]3− Keggin-type polyoxoanion and three {(HDCD)}+ monocationic hydrogen-bonded units. The electrochemical behavior and electrocatalysis of 1 have been studied in detail.

Open‐Framework Beryllium Hydrogen Phosphates with (3,4)‐Connected Networks

Four beryllium hydrogen phosphates, Be2(Hea)(PO4)(HPO4) (1), Him·Be3(OH)(HPO4)3 (2a), Hpy·Be3(OH)(HPO4)3 (2b), and Hma·Be1.5(HPO4)2·0.5H2O (3) in which ea = ethanolamine, im = imidazole, py = pyridine, and ma = methylamine, were synthesized under solvothermal conditions. All compounds have open-framework structures with (3,4)-connected networks. Compound 1 features a neutral inorganic–organic hybrid framework with an interrupted zeolitic GIS topology. The dual role of the amine molecules as charge-balancing agents and coordinating agents to the beryllium atoms is noteworthy. Compounds 2a and 2b are isostructural, and they have an AFI-related framework with elliptical 12-ring channels. Compound 3 has a 3D structure with 4.82 layers pillared by corner-sharing four-ring chains. It represents the first example of an open-framework beryllium hydrogen phosphate with 16-ring channels.

Two Tetra-CdII-Substituted Vanadogermanate Frameworks

Two new tetra-Cd(II)-substituted vanadogermanate frameworks {(CdX)4Ge8V(IV)10O46(H2O)[V(III)(H2O)2]4(GeO2)4}·8H2O (X = ethylenediamine (en, 1) and 1,2-diaminopropane (dap, 2)) were hydrothermally prepared and characterized by IR spectra, elemental analysis, powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and X-ray single-crystal diffraction. Both are isomorphic, and their 3-D frameworks are made up of tetra-Cd(II)-substituted {(CdX)4Ge8V(IV)10O46(H2O)}(12-) fundamental building units interconnected through planar tetra-V(III) [V(III)4O2(H2O)8](8-) clusters and tetrahedral GeO4 bridges. In the unique {(CdX)4Ge8V(IV)10O46(H2O)}(12-) cage, four [Ge2O7] dimers and four CdO4N2 trigonal prisms are alternately concatenated by μ3-O bridges to create a round {Ge8Cd4O28(X)4}(16-) fragment, five VO5 groups are linked by sharing edges to generate a pentanuclear [V5O17] subunit, and then the {Ge8Cd4O28(X)4}(16-) fragment is sandwiched by two V5O17 subunits via sharing O-atoms producing a D4h-symmetric {(CdX)4Ge8V(IV)10O46(H2O)}(12-) cage with a free water molecule located at the center. As we know, both display unprecedented 3-D organic-inorganic hybrid frameworks built up from the largest number of transition-metal-substituted vanadogermanate {(CdX)4Ge8V(IV)10O46}(12-) cluster shells linked by both GeO4 tetrahedra and rare [V(III)4O2(H2O)8](8-) clusters. Magnetic measurements reveal the antiferromagnetic couplings within the magnetic vanadium centers.

Acentric and chiral heterometallic inorganic–organic hybrid frameworks mediated by alkali or alkaline earth ions: synthesis and NLO properties

The rapid development in inorganic–organic hybrid frameworks has enabled the discovery of many structurally fascinating and technologically useful materials. The design of such hybrid crystals with noncentrosymmetric frameworks is particularly important because of their interesting electronic and optical properties. Several synthetic approaches, including the use of chiral and unsymmetric ligands, or spontaneous resolution via using achiral building blocks, have been applied to facilitate the formation of acentric and chiral hybrid materials. In this highlight, we will review another way to increase the chance of obtaining acentric and chiral frameworks by adding alkali or alkaline earth metals into heterometallic systems. The synthesis of these frameworks is discussed along with their potential NLO properties.

Hydrothermal Synthesis and Characterization of a Novel Lead(II) Inorganic-Organic Hybrid Framework Based on a Highly Flexible 2,2′-Thiodiacetic Acid Ligand

Under the hydrothermal conditions, based on a highly flexible H2L (2,2′-thiodiacetic acid) ligand and corresponding lead(II) salts, a novel lead(II) inorganic-organic hybrid framework {Pb3(μ8-L)2(μ2-Br)2}n (1) has been isolated. In 1, 1D infinite Pb-O-Pb and Pb-Br-Pb connectivity can be observed, which are interlinked forming a novel 2D inorganic-organic framework with I2O0type. The six-coordinated geometry of Pb1 in the hemidirected geometry and eight-coordinated geometry of Pb2 in the holodirected geometry in 1 also can be observed. TG analysis and solid-state fluorescent spectrum of 1 have also been investigated. The variable lead(II) geometries and coordination numbers together with flexible coordination modes of deprotonated 2,2′-thiodiacetate ligand also reveal great potential in the rational design and deliberate construction of those novel inorganic-organic hybrid materials. Supplementary material is available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.]

Novel Three-Dimensional Organic–Inorganic Heterometallic Hybrid Built by Sandwich-Type Tetra-Mn-Substituted Germanotungstates through Mixed 3d and 4f Metal Linkers

The reaction of trivacant Keegin germanotungstate [A-α-GeW9O34]10– with Mn2+ and Ce4+ cations in the presence of oxalate ligand under hydrothermal conditions led to the isolation of a novel organic–inorganic hybrid 3d–4f heterometallic germanotungstate K4Na4[Ce2(ox)3(H2O)2]2{[Mn(H2O)3]2[Mn4(GeW9O34)2(H2O)2]·14H2O (1) (ox = oxalate), which has been characterized by elemental analysis, IR spectroscopy, thermogravimetric (TG) analysis, and single-crystal X-ray crystallography. Interestingly, each tetra-MnII-substituted sandwich-type unit acts as 14-dentate ligands to link eight Ce3+ centers and six Mn2+ centers further into a three-dimensional (3D) architecture. The 3D structure can be considered as two parts: one is the two-dimensional layer formed by sandwich-type [Mn4(H2O)2(GeW9O34)2]12– fragments and Mn2+ linkers; the other layer is constructed from Ce3+ cations and oxalate bridges, and the two layers are combined together alternately through W–O–Ce–O–W linkers, resulting in the 3D framework. Notably, 1 exhibits the first 3d–4f 3D organic–inorganic hybrid framework constructed by sandwich-type TM-substituted polyoxoanions and mixed 3d and 4f metal linkers in POM chemistry.

Hydrothermal Synthesis and Characterization of a Novel 3D Chiral Inorganic-Organic Hybrid Cadmium(II) Framework With Achiral 1,4-Naphthalenedicarboxylic Acid Ligand

Using the achiral 1,4-naphthalenedicarboxylic acid (H2L) ligand and corresponding cadmium(II) salts, under hydrothermal conditions, a novel 3D chiral inorganic-organic hybrid complex with the formula [Cd(μ6-L)(DMF)]n has been isolated and characterized by single-crystal X-ray diffraction, FT-IR, TGA, and luminescent analysis. The crystal crystallizes in the chiral space group P212121, a = 6.7180(10) Å, b = 13.507(2) Å, c = 15.229(2) Å, Z = 4, the flack parameter is near zero (–0.02(4)). Two kinds of 1D infinite right-handed Cd-O-Cd helical chains can be observed, which are further interlinked into 1D infinite Cd-O-Cd linkage in a unique arrangement way. Solid-state luminescent spectrum of 1 also has been investigated indicating the strong emission band centered at 494 nm upon excitation at 370 nm. The result also represents a good example of the construction of those chiral inorganic-organic hybrid frameworks containing infinite M-O-M linkage using the achiral precursor. Supplementary materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.

A new acentric heterometallic inorganic–organic hybrid framework with an unusual {Cd3Na4}n array: NLO and ferroelectric properties

By employing 1,1′-biphenyl-3,3′-dicarboxylic acid (3,3′-H2BPDA) as a bridging ligand, a novel acentric heterometallic inorganic–organic hybrid framework [Cd3Na4(3,3′-BPDA)5(DME)7]·DME (1) has been synthesized. Single crystal X-ray diffraction study reveals that 1 contains an unusual 1D {Cd3Na4}n motif which is further extended into a 2-fold interpenetrating layer by trans-coordinated 3,3′-BPDA2− ligands. Compound 1 is NLO active with a SHG effect being 0.5 times that of KDP. Besides, it also displays a potential ferroelectric property.

Synthesis and Characterization of a Novel Luminescent Silver(I)-Chromium(III) Heterometallic Hybrid Material With a Tripodal Ligand N-(Carbamoylmethyl) Iminodiacetato Acid (H2ADA)

Using the tripodal N-(carbamoylmethyl)iminodiacetato acid (H2ADA) ligand and corresponding Ag(I) and Cr(III) salts, a novel two-dimensional (2D) heterometallic Ag(I)-Cr(III) coordination polymer [AgCr(ADA)2]n (1) has been isolated. H2ADA are deprotonated into ADA2−, which adopts a novel asymmetrical η1, η1, η1, η2, μ5-pentadentate coordination mode to bridge neighboring seven-coordinated Ag(I) and five-coordinated Cr(III) ions forming a 2D inorganic-organic hybrid framework containing 2D Ag-O-Cr inorganic connectivity. The solid-state fluorescence spectrum of 1 was also investigated exhibiting the maximum emission peak at 609 nm while no fluorescence emission band can be observed for the free ligand. 1 also represents a luminescent heterometallic hybrid framework with scarcely reported pentacoordinated deprotonated H2ADA ligands. Supplemental materials are available for this article. Go to the publisher's online edition of Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry to view the supplemental file.

A Luminescent Rod-Packing Organic–Inorganic Hybrid Framework Based on Copper(I) Cyanide Ribbon and 5-(4-Pyridine)tetrazole Ligand

The hydrothermal reaction of CuCN, K3Fe(CN)6 and 5-(4-pyridine)tetrazole generated a novel three-dimensional organic–inorganic hybrid framework, namely, {Cu3(5PyTAZ)(CN)2}n (1) (5PyTAZ = 5-(4-pyridine)tetrazole). X-ray single-crystal diffraction shows that two independent Cu(I) centers are four-coordinate tetrahedral and three-coordinate trigonal geometries, which are connected by μ3-CN groups to form a 1D [Cu3(CN)2]n inorganic ribbon along the c-axis direction. Each 5PyTAZ ligand links four adjacent inorganic ribbons via its five N-atoms to generate a complex 3D hybrid structure. If the 1D copper(I) cyanide ribbon was regarded as rod-shape building block, 1 exhibits a simple rod-packing topological framework. Furthermore, 1 is characterized by X-ray powder diffraction, elemental analysis, FT-IR, Raman spectra and TG/DTA. Notably, solid-state luminescence measurements indicate that 1 is a potential photoluminescence material.

An inorganic–organic hybrid material {[Dy2(SO4)(Himdc)2(H2O)5]·H2O}n featuring organic carboxylic acid and inorganic sulfate and luminescent property

Abstract Hydrothermal treatment of a mixture of H3imdc (4,5-imidazoledicarboxylic acid), Na2SO4, Dy(NO3)3·6H2O and NaOH generated a novel inorganic–organic hybrid framework, {[Dy2(SO4)(Himdc)2(H2O)5]·H2O}n (1). Its crystal structure contains alternately arranged 1D left- and right-handed helical {Dy(Himdc)}n chains, each helical chain is composed of alternately arranged Dy(1) and Dy(2) ions connected by Himdc2– with bis(bidentate) linking mode. Every three helical chains are bridged by inorganic SO42 − anions, which link Dy3 + ions in a tris(monodentate) mode to form a 3D framework. Compound 1 displays intense yellow photoluminescence corresponding to the characteristic 4F9/2 → 6HJ transitions of the Dy3 + ion.

Hydrothermal syntheses and characterization of a series of lead(II) inorganic–organic hybrid frameworks tuned by reaction temperature and inclusion of halide anions

Abstract Based on a highly flexible H2L (2,2′-thiodiacetic acid) ligand and corresponding lead(II) salts, a series of novel lead(II) inorganic–organic hybrid frameworks {[Pb2(μ6-L)(μ7-L)]}n (1), [Pb(μ6-L)]n (2) and {Pb3(μ8-L)2(μ2-Cl)2}n (3) have been isolated under hydrothermal conditions. 1 and 2 represent a novel example of tuning the inorganic–organic hybrid frameworks from I1O1 type to I2O0 type and coordination geometries of lead(II) via changing the hydrothermal reaction temperature. When halide chloride anions were introduced into the reaction system, another novel hybrid framework 3 can be isolated. In 3, 1D infinite Pb–O–Pb and Pb–Cl–Pb connectivity can be observed, which are inter-linked forming another type of 2D inorganic–organic framework with I2O0 type. Four different coordination modes of full de-protonated L2 − ligand can be observed in 1–3. The variable lead(II) geometries and coordination numbers together with flexible coordination modes of de-protonated L2 − ligand also reveal great potential in the rational design and deliberate construction of those novel inorganic–organic hybrid materials.

Synthesis and Structure of Two Acentric Heterometallic Inorganic–Organic Hybrid Frameworks with Both Nonlinear Optical and Ferroelectric Properties

Solvothermal reactions of Cd(NO3)2·4H2O with aromatic polycarboxylic acids in the presence of sodium nitrate led to two acentric three-dimensional (3D) heterometallic inorganic–organic hybrid frameworks, namely, [Me2NH2][Cd2Na3(2,4-PYDC)4]·2H2O (1) and [Me2NH2] [CdNa(OH-m-BDC)2(H2O)2]·2H2O (2) (2,4-H2PYDC = 2,4-pyridinedicarboxylic acid, OH-m-H2BDC = 5-hydroxyisophthalic acid). The framework of 1 is constructed by a 3D inorganic Cd–Na connectivity, which resembles a concrete reinforcement structure and features a {CdNa}n rod-shaped chain, a {CdNa2}n helical chain, and a 20-membered {Cd6Na14} ring. Compound 2 is built up by one-dimensional inorganic {CdNa}n rod-shaped chains which are further connected by OH-m-BDC2– ligands, affording a 3D polymeric framework. Compounds 1 and 2 crystallize in acentric space groups, and both display powder second harmonic generation efficiencies approximately 0.8 and 0.7 times, respectively, than that of the potassium dihydrogen phosphate (KDP) powder. In addition, they also exhibit luminescence and potential ferroelectric properties.

Hybrid Inorganic–Organic Framework as Efficient Heterogeneous Catalyst for the Synthesis of Allyl Glycidyl Carbonate from CO<SUB>2</SUB> and Allyl Glycidyl Ether

A mixed-linker nanoporous coordination polymer Zn2(HIP)2(bipy)(H2O)2 x H2O (ZnHipBipy) constructed from polyfunctional linker 5-hydroxy isophthalic acid (HIP) and exo-bidentate ligand 4,4'-bipyridyl (bipy) was employed as heterogeneous catalyst for allyl glycidyl carbonate (AGC) synthesis from CO2 and allyl glycidyl ether (AGE) under solventless conditions. Besides being the organic linker, 5-hydroxy isophthalic acid enriches the functionality of the material through accessible hydroxyl group capable of contributing extensive hydrogen bonding interactions. The cycloaddition of CO2 and epoxide was catalyzed through a synergistic pathway offered by inherent hydroxyl group together with the catalytically active metal centre. Method of synthesis and texture of the catalyst were key factors in determining the conversion and selectivity. The effects of reaction parameters like catalyst amount, temperature, CO2 pressure and reaction time on the yield of AGC were also studied.