Organic-inorganic Hybrid Complexes Research Articles

Self-assembly of two Keggin-based 3D and 2D complexes with cobalt (II)-bis(triazole) motifs: Influenced by the spacer length of the ligands

Two Keggin-based inorganic–organic hybrid complexes, [Co2(H2O)2(btb)4(HPMoVI10MoV2O40)] (1) and [Co2(btx)5(HPMoVI10MoV2O40)] (2) (btb=1,4-bis(1,2,4-triazol-1-yl)butane, btx=1,6-bis(1,2,4-triazol-1-yl)hexane), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, and thermogravimetric analyses (TGA). Complex 1 exhibits 2D ladder-like metal–organic layers, which are further linked by the Keggin anions to construct a 3D twofold interpenetrating framework. Complex 2 shows a 2D metal–organic network containing two kinds of pores, in which the Keggin anions acting as bidentate inorganic linkages reside alternately. The flexible bis(triazole) ligands btb and btx with different spacer lengths play an important role in the formation of the final structures. In addition, the electrochemical and photocatalytic properties of 1 and 2 have been reported.

Heterometallic, Hybrid, Heavy Main‐Group Iodometallates Containing Lanthanide Complexes: Template Synthesis, Structures, Thermal, Optical, Luminescent and Magnetic Properties

AbstractUsing [Ln(L)8]3+ [Ln = Tb, Y; L = dimethyl sulfoxide (DMSO), N,N‐dimethylformamide (DMF)] cations as templating reagents, the syntheses and crystal structures of the following new metal organic–inorganic hybrid complexes based on either discrete clusters or 1D chains of an iodoplumbate or‐bismuthate moiety are reported: [Tb(DMSO)8]2[(DMSO)2Pb5I16] (1), [Tb(DMF)8][Pb3I9]1∞·DMF (2) and [Ln(DMF)8][Bi2I9] [Ln = Y (3), Tb (4)]. These derivatives were characterized by thermogravimetric analysis (TGA), diffuse‐reflectance spectroscopy, luminescence spectroscopy and magnetic studies. TGA studies show that the thermal stability of these complexes decreases in the order 2 > 3 ≈ 4 > 1. An optical band‐gap in the range 1.90–2.15 eV in the diffuse‐reflectance spectra of 1–4 indicate their potential use as semiconductors, 3 and 4 being the most promising because of their low band gap values. Compared to the precursors [Tb(DMSO)8]I3 and [Tb(DMF)8]I3, the high energy transitions in the excitation spectra of 1, 2 and 4 are quenched by a process that is best attributed to the autoionization of the carriers in the material. The temperature dependence of the magnetic susceptibilities of 1, 2 and 4 was reproduced well by a Curie–Weiss plot at 2–300 K.

Exploring supramolecular interactions between inorganic tetrachlorometallate and organic pyridinium dication: Synthesis, characterization and structural investigations

Abstract The crystal structures of three isostructural salts 2, 3 and 4 consisting of dication (α,α′-p-xylylene-N,N′-bis(3-hydroxymethylpyridinium) (L2+)), and tetrachlorometallates, [MCl4]2− (M = Co(II), Zn(II) and Cu(II) in 2, 3 and 4 respectively) have been reported. Synthesized salts are well characterized by various physico-chemical techniques such as CHN analysis, IR, TGA, DSC, NMR, PXRD and single crystal X-ray diffraction. The crystal lattice of complex 2 is constructed from two types of interactions viz., C–H⋯Cl and O–H⋯Cl H-bonding between the pyridinium dication and the complex anions [CoCl4]2−, whereas only C–H⋯Cl interaction was found to play major role in stabilizing the structures of organic inorganic hybrid complexes 3 and 4. The hierarchy of intermolecular interactions present in solid state, factors controlling the adopted structures of these compounds and their thermal stability are discussed in detail by using various analytical techniques including single crystal X-ray.

Thermal-induced dynamic self-assembly of adenine-grafted polyoxometalate complexes

A new kind of organic-inorganic hybrid complexes based on polyoxometalate were synthesized through symmetrically grafting two adeninyl groups onto Anderson-type MnMo(6) clusters and encapsulating the clusters by organic surfactants. The resultant complexes exhibited thermal-induced dynamic self-assembly behaviors which greatly depended on the ambient temperature and the chain length of cationic surfactants. With the encapsulation of a short surfactant tetrabutyl ammonium, the complex assembled into fibrous, rod-like, and tubular architectures respectively upon heating; while for the case of using a long surfactant dimethyldioctadecyl ammonium as counter ions, the assemblies of the complex transformed from fibers to spheres with the increased temperature. Moreover, the two types of transformations were both reversible during a cooling process. The related mechanism was investigated by combining multiple characterization methods including X-ray crystallography, XPS, FT-IR and temperature-dependent (1)H NMR, which indicated that such a thermal-induced morphological transformation resulted from a synergy effect of the variation of the multiple hydrogen bonds among the complexes and the rearrangement of the surfactants surrounding the MnMo(6) clusters. These results demonstrated a new concept that hydrogen bonds can be rationally employed as the driving force for the fabrication of polyoxometalate-based materials with smart responsive properties.

Solid-state structural transformations in metal organic-inorganic hybrids constructed from terbium(iii) complexes and iodocuprate clusters

Using precursors of the type [Tb(DMSO)8]I3 (a) and [Tb(DMF)8]I3 (b), syntheses of two new heterometal organic–inorganic hybrid complexes based on discrete iodocuprate clusters [Tb(DMSO)8][Cu2I5] (1) and [Tb(DMF)8][CuI3][I] (2), respectively, are reported. Though stable in air for few days, the colorless complex 1 slowly turns into a purple-colored mixture over the course of several days. Two complexes, namely [Tb(DMSO)8][CuI3][I] (3) and [Tb(DMSO)8](I)2(I3) (4), were isolated from this mixture and characterized structurally, the I3− anion in latter being responsible for the purple color of this mixture. In comparison, complex 2 is quite deliquescent in air but undergoes solid state structural transformation in a confined environment of paratone to afford a 2D honeycomb-like microporous structure containing mixed-valent copper atoms [Tb(DMF)6(H2O)3][CuII2CuI7I14]2∞ (5), the bifurcate H-bonding between water ligands on terbium and iodides of the Cu–I cluster playing a pivotal role in the evolution of its structure. Single crystal X-ray structures are reported for all the complexes. Thermal and luminescent properties of 1 and 2, complexes, which were obtained exclusively and in pure form, are described. Compared to the precursor terbium iodide complexes (a) and (b), the high energy transitions in the excitation spectra of the complexes 1 and 2 are quenched by auto-ionization of the carriers in the material.

Structure and luminescence of [Tb0.5(C6NO2H5)3(H2O)2]2n ·(H3O)4n (ZnCl5) n (ZnCl4)2n

A novel bimetallic 4f-3d metal-isonicotinic acid inorganic-organic hybrid complex [Tb0.5(C6NO2H5)3(H2O)2]2n ·(H3O)4n (ZnCl5) n (ZnCl4)2n (1) is synthesized. It has a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that it displays interesting emissions in the violet, blue, green, and yellow regions.

ChemInform Abstract: Crystal Structures and Conductivities of Two Organic—Inorganic Hybrid Complexes Based on Poly‐Keggin‐Anion Chains.

AbstractCompounds (IIIa) and (IIIb) crystallize in the orthorhombic space group Pnnm with Z = 2 (single crystal XRD) and exhibit exactly the same three‐dimensional supramolecular framework built from non‐covalent interactions between isonicotinic acid N‐oxide (HINO) molecules, [M(H2O)8]2+ and H+(H2O)2.5 clusters, and [PMo12O40]3‐ anions which self‐assemble into poly‐Keggin‐anion chains.

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.

Crystal Structures and Conductivities of Two Organic–Inorganic Hybrid Complexes Based on Poly‐Keggin‐Anion Chains

AbstractTwo proton‐conducting organic–inorganic hybrid complexes have been constructed by the self‐assembly of protonated water clusters, transition‐metal aqua ions, [PMo12O40]3– anions and isonicotinic acid N‐oxide (HINO). Single‐crystal X‐ray diffraction analyses at 293 K revealed that both complexes presented exactly the same three‐dimensional supramolecular framework built from non‐covalent interactions. Interestingly, the [PMo12O40]3– anions self‐assembled into poly‐Keggin‐anion chains in the supramolecular frameworks. Thermogravimetric analyses showed no weight loss for either system in the temperature range of 20–100 °C, which indicates that none of the water molecules in the unit structure are easily lost below 100 °C. Surprisingly, the proton conductivities of 1 and 2 in the temperature range of 85–100 °C under 98 % relative humidity reached good proton conductivities of 10–3 S cm–1. A possible mechanism for the proton conduction in accord with experimental results is proposed.

Three organic–inorganic hybrid complexes based on the Wells–Dawson polyoxoanion

Three new organic–inorganic hybrid complexes based on the Wells–Dawson polyoxoanion, namely (H2bpp)[Ni2(bpp)2(H2O)4(P2W18O62)]·H2O 1, [Cu6(Hbpy)6(bpy)3(P2W18O62)2]·2H2O 2 and (Him)5[Cu(im)2(P2W18O62)]·4H2O 3 [bpp = 1,3-bis (4-pyridyl) propane, bpy = 4,4′-bipyridine, im = imidazole] have been synthesized and characterized. Complex 1 exhibits a three-dimensional (6, 3)-connected framework with anatase topology constructed from [α-P2W18O62]6− clusters and [Ni(bpp)]2+ fragments. Each [α-P2W18O62]6− anion links to six nickel atoms through six terminal oxygen atoms from four polar and two equatorial WO6 octahedra, which shows a novel coordination mode of a Wells–Dawson cluster with a transition-metal atom. Complex 2 displays an interesting one-dimensional double-chain structure built from [α-P2W18O62]6− clusters and [Cu2(bpy)(Hbpy)2]2+ fragments. To our knowledge, complex 2 represents the first double-chain organic–inorganic hybrid complex based on a Wells–Dawson-type cluster. Complex 3 possesses a one-dimensional zigzag chain structure constructed from [α-P2W18O62]6− anions and [Cu(im)2]+ units through weak Cu···O interactions.

ChemInform Abstract: Construction of Some Organic—Inorganic Hybrid Complexes Based on Polyoxometalates

AbstractReview: 55 refs.

A rubidium organic-inorganic hybrid complex with channels hosting decorated polyanion chains

A rubidium organic-inorganic hybrid complex, {H2[Rb(PMo12O40)(CH3CN)3](dpdo)2(H2O)2} n (1), (where dpdo is 4,4′-bipyridine-N,N′-dioxide) with special channels for the chainlike assembly of decorated Keggin-type anions was synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is Orthorhombic space group Cmcm with a = 20.4713(18) A, b = 17.0529(15) A, c = 16.1968(14) A, V = 5654.2(9) A3, Z = 4, C26H31N7O46RbMo12P, M = 2445.30, D c = 2.873 Mg m−3, μ = 3.570 mm−1, F(000) = 4640, the final R = 0.0438 and wR = 0.1350 for 2065 observed reflections with I > 2σ(I). Compound 1 exhibits a 3D network with large channels hosting decorated polyanion chains as guests.

Poly[{μ10-[(phosphonomethyl)iminodimethylene]diphosphonato}dithallium(I)

The title compound, [Tl2(C3H10NO9P3)]n, a TlI organic–inorganic hybrid complex, was synthesized by the reaction of nitrilo­tris(methyl­enephospho­nic acid) with thallium(I) nitrate. There are two types of Tl+ ions in the complex, with coordination numbers of eight and seven and with stereochemically active and inactive lone-pair electrons, respectively. In the crystal, the doubly deprotonated ligands form two-dimensional hydrogen-bonded layers through O—H⋯O hydrogen bonds. The NH group is involved in a trifurcated intra­molecular hydrogen bond. Coordination of the phospho­nate ligands to the Tl+ ions creates a three-dimensional structure.

Certain New Organic-Inorganic Hybrid Complexes of Monobutyltin(Iv) of ß-Diketones / Fluorinated ß-Diketone and Sterically Congested Heterocyclic ß-Diketones : Preparation, Structural Chemistry and Structural Elucidation Based upon Spectroscopic [Ir and Nmr (1Η, 13C and 119Sn)] Studies

Certain New Organic-Inorganic Hybrid Complexes of Monobutyltin(Iv) of ß-Diketones / Fluorinated ß-Diketone and Sterically Congested Heterocyclic ß-Diketones : Preparation, Structural Chemistry and Structural Elucidation Based upon Spectroscopic [Ir and Nmr (1Η, 13C and 119Sn)] Studies

New Organic-Inorganic Hybrid Complexes of Aluminium (Iii) of B-Diketones and Sterically Demanding Heterocyclic B-Diketones: Synthesis, Structural Aspects and Spectroscopic [Ir and Nmr (1h, 13c and 27al)] Characterization

New Organic-Inorganic Hybrid Complexes of Aluminium (Iii) of B-Diketones and Sterically Demanding Heterocyclic B-Diketones: Synthesis, Structural Aspects and Spectroscopic [Ir and Nmr (1h, 13c and 27al)] Characterization

Synthesis, crystal structure and properties of [Nd(C6NO2H5)3(H2O)2]2n · (nH5O2)(nHgCl5)(2nHgCl4) · (nH2O) with unprecedented polycationic chains

A novel inorganic-organic hybrid complex, [Nd [Nd (C6NO2H5)3(H2O)2]2n · (nH5O2)(nHgCl5)(2nHgCl4) · (nH2O)(1), was obtained by hydrothermal reactions and structurally characterized by X-ray diffraction. The unit cell parameters are as follows: a = 9.579(1), b = 21.462(2), c = 15.801(1) A, β = 102.339(6)ℴ, V = 3173.5(5) A3, Z = 4, space group P21/c. The crystal structure analysis reveals that the title complex is characteristic of a novel polycationic [Nd(C6NO2H5)3(H2O)2]2n6n+ one-dimensional chain-like structure. Photoluminescent investigation shows that the title complex displays strong emission in blue region, which is attributed to the intraligand π-π*-transition of nicotinic ligands. Optical absorption spectra of 1 reveal the presence of an optical gap of 3.45 eV.

Synthesis, structure, and properties of [Gd(C6NO2H5)3(H2O)2]2 n · ( n H5O2)( n ZnCl5)(2 n ZnCl4) · (2 n H2O) with strong fluorescence

A 1-D metal-isonicotinato inorganic–organic hybrid complex [Gd(C6NO2H5)3(H2O)2]2 n · (nH5O2)(nZnCl5)(2nZnCl4) · (2nH2O) (1) has been synthesized via hydrothermal reaction and structurally characterized by single-crystal X-ray diffraction. Complex 1 is a 1-D polycationic chain-like structure with unprecedented . Optical absorption spectra of 1 reveal the presence of an optical gap of 3.35 eV. Photoluminescence investigations reveal that the complex 2 display a strong blue-light fluorescent emission band.

A three-dimensional hybrid framework based on novel [Co4Mo4] bimetallic oxide clusters with 3,5-bis(3-pyridyl)-1,2,4-triazole ligands

In the title organic-inorganic hybrid complex, poly[[[mu-3,5-bis(3-pyridyl)-1,2,4-triazole]tri-mu(3)-oxido-tetra-mu(2)-oxido-oxidodicobalt(II)dimolybdenum(VI)] monohydrate], {[Co(2)Mo(2)O(8)(C(12)H(9)N(5))].H(2)O}(n), the asymmetric unit is composed of two Co(II) centers, two [Mo(VI)O(4)] tetrahedral units, one neutral 3,5-bis(3-pyridyl)-1,2,4-triazole (BPT) ligand and one solvent water molecule. The cobalt centers both exhibit octahedral [CoO(5)N] coordination environments. Four Co(II) and four Mo(VI) centers are linked by mu(2)-oxide and/or mu(3)-oxide bridges to give an unprecedented bimetallic octanuclear [Co(4)Mo(4)O(22)N(4)] cluster, which can be regarded as the first example of a metal-substituted octamolybdate and exhibits a structure different from those of the eight octamolybdate isomers reported to date. The bimetallic oxide clusters are linked to each other through corner-sharing to give two-dimensional inorganic layers, which are further bridged by trans-BPT ligands to generate a three-dimensional organic-inorganic hybrid architecture with six-connected distorted alpha-Po topology.

Crystal Structure of Bis(5-Chloro-2,4-Dimethoxyanilinium) Tetrachlorozincate Trihydrate

The new inorganic-organic hybrid complex of Zn(II) with 5-Chloro-2,4-dimethoxyaniline, (5-Cl-2,4- (OCH3)2C6H2NH3)2ZnCl4.3H2O, has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic space group P1 with a = 7.4614 (2), b = 9.8734 (2), c = 18.5678 (4) A,  = 102.3578 (14),  = 91.0686 (15),  = 91.2373 (12)°, V = 1335.49 (5) A 3 , Z = 2. Crystal structure has been determined and refined to R = 0.035 and Rw = 0.036 using 5107 independent reflections. In the atomic arrangement of the title compound, ZnCl4 2- inorganic entities, water molecule and -NH3 + groups have a layered organization around the planes z = 1/4 and z = 3/4. The crystal structure

Hydrothermal syntheses and structures of three novel coordination polymers assembled from 1,2,3-triazolate ligands

Three new coordination polymers with 1,2,3-triazolate ligands, [Cd3(ta)3Cl3]n (1), {[Cd3(ta)6]·6H2O}n (2) and [Cu6(ta)3I3]n (3) (Hta = 1,2,3-triazole), have been hydrothermally synthesized and structurally characterized. In complex 1, the Cd2+ and Cl− ions form a 3D [(Cd3Cl3)3+]n inorganic framework with (82.12)(4.8.10) topology while the Cd2+ ions and ta− ligands give a {[Cd3(ta)3]3+}n double helical chain. The two moieties are fused with each other by sharing “hinge” Cd2+ ions leading to a 3D organic–inorganic hybrid structure. The 3D porous metal–organic framework of complex 2 shows the topology of the diamond net with the Cd-centered CdCd4 tetrahedron units as the connecting nodes. The desolvated structure of 2 has 48% solvent accessible space of the total volume. Complex 3 is an undulating 1D organic–inorganic hybrid complex consisting of interesting discrete five-capped [Cu6I5]− triangular prism clusters and arched metallacycle [Cu6(ta)6I]+ moieties.