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Construction of viologen cation salts of d10 metal halide anions (inorganic-organic hybrid materials) with semiconducting properties via supramolecular design and aggregate enable the hybrid materials multifunctionality. Our interest focused on the use of the viologen derivatives as the building units because they were redox-active units and more suited to yield new generation of multifunctional networks. In the present investigation, three new inorganic-organic hybrid semiconductors {[bbpyb]·[AgBr3]}n (1) [1, 3-PMBP][Zn2Cl5.1Br0.9] (2) and [1, 3-PMBP][Zn2Br6] (3) (bbpyb = 1,1″-(1,4-butanediyl)bis[4,4′-bipyridinium]bis[bromide], 1,3-PMBP = 1,1″-[1,3-phenylene-bis(methylene)]bis-4,4′-bipyridinium-bisbromide) were synthesized. More importantly, great efforts were devoted to investigate their properties, such as optical and electrical properties. 1–3 exhibited photochromism, which can be ascribed to the intermolecular charge transfer to yield radicals. Fabricating the appropriate inorganic and organic units controllably within photosensitive materials at a molecular level is critical for the development of new photochromic inorganic-organic hybrids.

A series of organic–inorganic polypseudorotaxanes based on Cux(SCN)y polyanionic ring and bis(3,5-lutidine)alkyl dication threads are reported. This kind of interesting bis(pyridinium)alkyl template may facilitate the formation of 2D polypseudorotaxane. All these complexes exhibit excellent photochemical properties.

A new nanocrystalline inorganic-organic hybrid semiconductor [(BV)2(Ag5Br9)]n (1) with an intriguing windmill-like 1-D [Ag5Br9]n(n-) polymeric chain was assembled. Great efforts were devoted to investigate its semiconducting properties and applications, such as photoluminescence, emission decay lifetime, waste water purification, electrochemistry behavior and dielectric properties.

Compound {(MoOS3Cu3Br(-bpy)2.5)·0.75DMF}∞ is an isomorphous neutral 3D 4-fold interpenetrating architecture displaying self-interpenetrating feature.sometimes, the compound like the art. All of it have been characterized by single-crystal X-ray diffraction, elemental analysis, IR, TGA, and UV-vis. The results may provide fascinating insights into template effect on the construction of the cluster-based coordination polymers.

The N-1-methylimidazole-substituted multication-templated self-assembly of CuSCN/AgSCN leads to five novel complex salts: {(tbi)[Cu3(SCN)6]}n (1), {(tbmi)[Cu2(SCN)5]}n (2), {(tebi)[Cu(SCN)2]4}n (3), {(tebi)[Cu(SCN)2]4}n (4) and {(tbmi)2[Ag5(SCN)11]}n (5) [tbi3+ = 1,3,5-tri[3′(1′-methyl)imidazoliummethyl]benzene, tbmi3+ = 1,3,5-tri[3′-(1′-methyl)imidazoliummethyl]-2,4,6-trimethylbenzene and tebi4+ = 1,2,4,5-tetra[3′-(1′-methyl)imidazoliummethyl]benzene]. Single-crystal X-ray diffraction shows that 2, 3 and 5 display a 2D sandwich structure, 4 presents a 2D polypseudorotaxane network, whereas, 1 exhibits a 3D polypseudorotaxane architecture. It is worth noting that SCN− can present five coordinating modes. All these results confirm the versatile template effect and correct choice of multications. In addition, elemental analysis, IR and UV–Vis spectra, powder X-ray diffraction patterns, thermogravimetric analyses of these complexes have been investigated.

The solvothermal reaction of a mixture of bismuth iodide, flexible cationic compound 1,1″-(1,4-butanediyl)bis[4,4′-bipyridinium] bis[tetrafluoroborate] (bbpyf) and HI at the temperature of 110 °C resulted in a novel compound, namely [bbpy][Bi4I16] (1). The structure of compound 1 was explored with IR spectroscopy, thermal gravimetric analysis (TGA), PXRD, UV–vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. Compound 1 was a 2D supramolecular structure consisted of one linear cationic compound bbpy2+ and inorganic anion cluster [Bi4I16]2− and contained a channel of 11.214 × 9.727 A via noncovalent interactions. In addition, the adsorption behavior of 1 was also investigated. And it could adsorb methylene blue (MB) and Rhodamine B (RhB) from waste water fast and effectively, highlighting its potential application for environmental issues.

Three metal halide cluster supramolecular polymers, {(TBP)[Ag3Br6]}n (1), {(TBI)[Ag3Br6]}n (2) and {(TBP)[Ag3I6]}n(3) (TBP =1, 3, 5-tris(N-pyridinium methyl)benzene, TBI =1, 3, 5-tris(methylimidazole methyl)benzene), have been synthesized and characterized by thermoanalysis and spectroscopic methods, as well as single-crystal X-ray diffraction. Complexes 1, 2 and 3 all feature a one-dimensional chain structure, which is further extended by electrostatic attraction. The TGA, UV-Vis diffuse reflectance spectra in the solid state and optical band gap properties of the three complexes were also investigated.

Two novel cation-templated complexes, {(1, 4-PMBP)[Pb4I10] ⋅DMF}n(1) {(DBBP)2[Pb5I8Br6]}n(2), (1,4-PMBP ⋅2Br =1,1”-[1,4-phenylene-bis(methylene)]bis-4,4’-bipyridinium dibromide; DBBP ⋅2Br = N, N’-dibenzyl- 4, 4’-bipyridinium dibromide) have been synthesized via the self-assembly reaction in solution. X-ray crystallography showed that compounds 1 and 2 can be regarded as 1D iodoplumbate examples which contain incomplete cubane subunit directed by π-conjugated dication templates. It is the H-bonds and electrostatic interactions between the organic counter cations and inorganic moieties that contribute the crystal packing. These compounds have been further characterized by IR spectroscopy, UV-Vis spectra, elemental analysis and thermostability properties.

Four novel extended supramolecular structures based on pseudohalides (SCN) and the flexible cationic ligand 1,4-bis(4,4′-bipyridinium)butane ditetrafluoroborate (bbpyb), namely [bbpyb][Hg(SCN)4] (1), [Cu2(bbpyb)(SCN)4]n (2), [Ag2(bbpyb)(SCN)4]n (3) and [Cu6(bbpyb)(SCN)8]n (4) have been solvothermally synthesized and characterized by IR spectroscopy, thermal gravimetric analysis(TGA), PXRD, UV–Vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. Compound 1 is a 0D supramolecular structure consisted of one linear cationic ligand bbpyb2+ and inorganic mononuclear anion [Hg(SCN)4]2−. Compounds 2 and 3 exhibit infinite two-dimensional anionic architecture, which represent the same (6,3) topology. In compound 4, the cationic ligand bbpyb2+ bridge [Cu6(SCN)8] cluster unit to generate a 3D coordination framework. The structural diversities show that the pseudohalides (SCN) and cationic ligand should very likely be excellent candidates to construct higher dimensional extend supramolecular architectures. In addition, the optical band gap and photocatalytic properties of compounds 1–4 were also investigated.

A novel inorganic–organic hybrid polyoxometalate, [1,1′-dibutyl-4,4′-bipyridinium,][α-Mo8O26]0.5 (1), has been synthesized by the cation-templated self-assembly with octamolybdate anions under hydrothermal reaction conditions. The structure has been determined by single-crystal X-ray diffraction analysis and further characterized by PXRD, IR spectra, and elemental analysis. The crystal data analysis revealed that the compound was composed of one discrete [1,1′-dibutyl-4′-bipyridinium]2+ cation and 0.5 polyacid anions [Mo8O26]4– interacted by electrostatic interactions. In the compound the anion fraction take on a [α-Mo8O26]4– cluster.

Two Ag (I) photoresponsive metal–organic complexes have been constructed from viologen derivatives 1, 1″-[1, n-phenylene-bis(methylene)]bis-4, 4′-bipyridinium-bisbromide (n = 2 and 3) cationic ligands and silver bromide upon slow self-assembly at room temperature. They are characterized by single crystal X-ray diffraction, powder X-ray diffraction, thermal gravimetric analysis (TGA), UV–vis, IR and ESR spectra. Compound 1 is a 3D folding framework and compound 2 contains a 1D inorganic chain constructed by (AgBr3)2 − polyhedral units. In addition, the photochromic behaviors of compounds 1 and 2 were also investigated, and they show different and obvious fast photoresponse rate under sunlight.

The hydrothermal reaction of a mixture of (NH4)6Mo7O24·4H2O, a flexible tripodal ligand 1,3,5-tris-(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (TITMB) and metal salts at different temperatures resulted in four novel compounds, namely [H2TITMB]2[Mo12O38]·4H2O (1), [Zn(Mo2O7)(TITMB)] (2), [H3TITMB]2[Cd(β-Mo8O26)(H2O)2(α-Mo8O26)]·4H2O (3) and [H3TITMB]2[Co(β-Mo8O26)(H2O)2(α-Mo8O26)]·4.5H2O (4). The structures of compounds 1, 2, 3 and 4 were explored with IR spectroscopy, thermal gravimetric analysis (TGA), PXRD, UV-vis diffuse reflectance spectra and single-crystal X-ray diffraction in the solid state. In 1 the new type of isopolymolybdate unit [Mo12O38]4− shared ten distorted {MoO6} octahedra and two distorted {MoO5} tetragonal pyramid with four kinds of O atoms. And the unprecedented bimetallic oxide chain [Zn(Mo2O7)]n in compound 2 consisted of trigonal bipyramids and octahedra through sharing edges. Both compounds 3 and 4 are 3-D octamolybdate-based inorganic–organic hybrids consisting of the polyacid [α-Mo8O26]4− anions and novel infinite chains of [β-Mo8O26]4− anions covalently linked through [Cd(H2O)2]2+ groups or [Co(H2O)2]2+ groups. In addition, the electrochemical behavior and photocatalytic activities of the title compounds were also investigated.

Two novel complexes based on multivalent organic cations and PbI2, {(tbp)2[Pb3I12]}n (1) (tbp = 1,3,5-tri(N-pyridinium methyl)benzene tribromide) and {(tbpm)[Pb3I9]·H2O}n (2) (tbpm = 1,3,5-tri(4-methylpyridiniummethyl) benzene tribromide), have been synthesized and characterized by X-ray diffractometry. Compound 1 has a trinuclear structure and compound 2 presents a new 1D iodoplumbate. Photochemical studies reveal the good photocatalytic performances of the two iodoplumbate hybrids. Furthermore, the side chain's effect on the fabrication of the iodoplumbate and the photocatalytic performances was also investigated.

Eleven novel polyoxometalates, namely [1,1′-(alkane-1,ω-diyl)-bis(3-methylimidazolium)]m [Mo8O26][nH3O+]·xH2O (ω = 1–11; m = 1, 1.5, 2; n = 0, 1; x = 0, 1, 2) were synthesized by the self-assembly with octamolybdate anions under hydrothermal reaction conditions. The crystal data analysis revealed that these compounds were all composed of discrete methylimidazolium cations and polyacid anions [Mo8O26]4− interacted by electrostatic interactions and hydrogen bonds. Interestingly, the anions of these compounds took on single [β-Mo8O26]4− cluster, twin [β-Mo8O26]4− clusters, a δ-[Mo8O26]4− cluster and a rare 1D 1/∞[β-Mo8O26]4− polymeric chain with the modification of lengths of alkane components.

Eleven novel inorganic–organic hybrid polyoxometallates, namely, [1,2-bis(1,2-dimethylimidazole)methane]3[β-HMo8O26]2·[H3O+]2·7H2O (1), [1,2-bis(1,2-dimethylimidazole)ethane]2[β-Mo8O26]·H2O (2), [1,2-bis(1,2-dimethylimidazole)propane]2[α-Mo8O26] (3), [1,2-bis(1,2-dimethylimidazole)butane]2[γ-Mo8O26] (4), [1, 2-bis(1,2-dimethylimidazole) pentane]3[β-Mo8O26]2[H3O+]2 (5), [1,2-bis(1,2-dimethylimidazole) hexane]4[β-Mo8O26]2 (6), [1,2-bis(1,2-dimethylimidazole)heptane][Mo6O19] (7), [1,2-bis(1,2-dimethylimidazole) octane] [Mo6O19] (8), [1,3,5-tris[(1,2-dimethylimidazole-3-iumyl)benzene)]2[β-Mo8O26]1.5·2H2O (9), [1,3,5-tris[(1,2-dimethylimidazole-3-iumyl)-2,4,6-trimethyl benzene)]4 [α-Mo8O26]2 [Mo6O19]2·4H2O (10), [1,3,5-tris[imidazol-1-ylmethyl)-2,4,6-trimethyl benzene)]2 [β-Mo8O26] [Mo6O19] (11) were synthesized by the cation-templated self-assembly with octamolybdate or hexamolybdate anions under hydrothermal reaction conditions. Crystal data analysis revealed that these compounds were all composed of discrete organic cations and polyacid anions interacted by electrostatic and hydrogen bond interactions. Interestingly in these compounds the anion fraction could take on [β-Mo8O26]4− cluster, α-[Mo8O26]4− cluster, γ-[Mo8O26]4− cluster, [Mo6O19]2− cluster or two mixing kinds of polyoxomolybdate anions with the modification of lengths of alkane components or change the valence configuration of the templates.

Two new organic-inorganic hybrid materials based on Mo-polyoxometalates and N-heterocycle templates, namely [Ag3 (DIE)6][Mo12O36·ClO4]2 ·Cl (1), and [(IM)4NH4] [Mo12O36·ClO4] (2) [DIE = 1,2-diimidazoloethane, IM = imidazole] have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 possess the classical keggin-type heteropolyoxoanion with Cl as the center atom, and this is the first case. IR spectroscopy and gravimetric analysis were performed to further characterize these compounds.

Abstrct Four novel organic–inorganic hybrid materials based on Mo–POMs and organic templates, namely [DEB] [β-Mo8O26] [NH4]2 (1), [BMIM] [β-Mo8O26]0.5·H2O (2), [BMIM] [1D-Mo8O26]0.5 (3) and {3D-[Cu(DIE)2] [1D-Mo8O26]0.5}∞ (4) [DEB= 1,1′-diethyl-4,4′-bipyridinium, BMIM=1,1′-bis(1-methylimidazolium)methylene, DIE=1,2-diimidazoloethane] have been hydrothermally synthesized and characterized by elemental analyses, IR spectroscopy, thermal gravimetric analysis(TGA) and single-crystal X-ray diffraction. Both compounds 1 and 2 are POMs-based supramolecular compounds consisted of independent [β-Mo8O26]4− anions and [DEB]2+ or [BMIM]2+ organic cations. Compound 3 is the first external template example of Mo–POMs-based supramolecular network incorporated with novel 1/∞[β-Mo8O26]4− polymeric chains. Compound 4 is a rare supramolecular structure that contains octamolybdate 1/∞[β-Mo8O26]4− polymeric chains interconnected via DIE ligands to form a 3D net. Moreover, it was indicated that these polyacid compounds had definite catalytic activities on the probe reaction of acetaldehyde oxidation to acetic acid with H2O2.

The self-assembly reaction of organic cation and metal iodides yielded a novel binuclear coordination compound, namely [btx][Cu2I4](1) [btx = 1,6-bis(triethylmethylammonium)xylol], which is characterized by X-ray crystallography, IR spectroscopy, fluorescence spectra, and UV-vis absorption spectra. The compound 1 crystallizes in Monoclinic, space group P2(1)/c with a = 8.2246(12), b = 11.5843(17), c = 15.005(2), α = 90°, β = 94.218(2)°, γ = 90°. In the anion [Cu2I4]2−, each Cu center is triangularly coordinated by two μ 2-I(2) atoms and one terminal I(1) atom. The organic cationic [btx]2+ existed around it through supramolecular interactions.

Two novel organic–inorganic hybrid supramolecular compounds based on organic cations and POMs, namely, [py]2[Hpy]3[PMo12O40]·H2O (1) and [btx]2[Mo8O26]·H2O (2) [btx = 1,6-bis(triethylmethylammonium)xylol], have been hydrothermally synthesized and characterized by single-crystal x-ray diffraction, infrared (IR) spectroscopy, and thermal gravimetric analysis (TGA). The compound 1 crystallizes in the monoclinic, space group P2(1)/c with a = 17.7932(18) A, b = 19.427(2) A, c = 15.2515(16) A, β = 98.479(2)°. Compound 2 crystallizes in the triclinic, space group P-1 with a = 11.6245(8)A, b = 11.9573(13)A, c = 12.8756(10)A, α = 63.830(6)°, β = 75.285(5)°, γ = 68.024(5)°. Compound 1 contained the classical Keggin-type discrete [PMo12O40]3− anion and 2 had the a-[Mo8O26]4− cluster. Moreover, it was indicated that these polyacid compounds had definite catalytic activities on the reaction of acetaldehyde oxidation to acetic acid.

Six dication-templated complexes were discovered in efforts to investigate the effect of linear imidazolium-based template, 1,ω-bis(3,3′-methylimidazolium)alkyl dibromide, on pure inorganic halometal clusters. Complexes {[C4(Mim)2](Pb2I6)}n (1) (ω = 4), {[C1(Mim)2] (Ag2I4)}n (2) (ω = 1), {[C3(Mim)2](Ag2I4)}n (3) (ω = 3), and {[C4(Mim)2](Ag2I4)}n (4) (ω = 4) possess 1-D chain architecture with different organic cations trapped in it. Compound {[C3′(Mim)2](CuBr3)} (5) (ω = 3) contains the mononuclear anion (CuBr3)2− and intra-molecular coupled organic cation with the formed seven-membered ring. {[C2(Mim)2S2]2(Cu2I2)}n (6) (ω = 2) presents an infinite 2-D coordination polymer as the first representative polyrotaxane example featuring the biimidazolium thiolate cation ligand. All compounds were further characterized with IR spectra and thermal analysis properties.

Trication-templated assembly of POMs resulted in an unprecedented ι-type octamolybdate configuration. The ι-[Mo8O26]4− cluster is composed of five {MoO6} octahedra and three {MoO4} tetrahedra via an edge-sharing and corner-sharing arrangement to form a cabas-like cluster, which represents the ninth isomer of octamolybdates.

Ten novel inorganic–organic hybrid polyoxometalates, namely, [1,3-bis(pyridinium) propane]2[α-Mo8O26] (1), [1,4-bis(pyridinium)butane]2[1D-Mo8O26] (2), [1,5-bis(pyridinium)pentane]2[θ-Mo8O26] (3), [1,6-bis(pyridinium)hexane]2[1D-Mo8O26] (4), [1,7-bis(pyridinium)heptane]2[β-Mo8O26] (5), [1,8-bis(pyridinium)octane]2[θ-Mo8O26] (6), [1,9-bis(pyridinium)nonane]2[(α + β)-Mo8O26] (7), [1,10-bis(pyridinium)decane]2[β-Mo8O26] (8), [1,11-bis(pyridinium)undecane]2[β-Mo8O26] (9), [1,12-bis(pyridinium)dodecane]2[γ-Mo8O26] (10), (Scheme 1) were synthesized by cation templated self-assembly with octamolybdate anions under hydrothermal reaction conditions. Crystal data analysis revealed that these compounds were all composed of discrete organic cations and polyacid anions [Mo8O26]4− interacting by electrostatic and hydrogen bond interactions. Interestingly in these compounds the anion fraction could take on α-, β-, θ-, γ-[Mo8O26]4− 0D isomers or rare 1D- polymeric frameworks with a simple length modification of the alkane components. Moreover, these polyacid compounds had definite catalytic activities on the oxidation reaction of acetaldehyde to acetic acid and the relationship of structure/catalytic activities were initially demonstrated.