| Under hydrothermal conditions, a series of polyoxometalates constructed from Keggin [BW12O40]5- and [PW12O40]3- polyanions as building blocks were successfully synthesized, which were characterized by X-ray crystallography, spectroscopic, thermal properties and optics properties.â… . We obtained five novel organic-inorganic hybrids based on Keggin tungstoborates:1.{[Ni(phen)2(H2O)]2H(α-BW12O40)}·4H2O: size 0.19×0.15×0.13 mm. triclinic system, P-1 space group, a = 11.2965(6) (?), b = 13.5334(7) (?), c = 13.5538(7) (?),α= 67.9540(10)°,β= 74.7330(10)°,γ= 69.0290(10)°, V= 1773.36(16) (?), Z=1,R1 = 0.0430, wR2 = 0.1071. Compound 1 is a bisupported 0-D compound, and the molecules of 1 are stably packed together viaÏ€-Ï€stacking interactions of the phen groups to generate a 3-D supramolecule structure.2.[Cu(en)(phen)(H2O)]4[BW12O40]{[Cu(en)2(H2O)]2[Cu(en)(phen)(H2O)]2[Cu(en) (phen)]2[BW12O40]3]}·14H2O: size 0.26×0.21×0.17 mm, orthorhombic system, Pbca space group, a = 26.2608(14)(?), b = 25.8192(13)(?), c = 36.822(2) (?),β= 90°, V = 24967(2) (?), Z = 4, R1 = 0.0473, wR2 = 0.0951. Compound 2 represents the first trimer based on Keggin-type [BW12O40]5- anion.3.[Cuâ… (2,2'-bipy)(4,4'-bipy)0.5]2{[Cuâ… (2,2'-bipy)]2Cuâ… (4,4'-bipy)2(α-BW12O40)}: size 0.18×0.15×0.12 mm, triclinic system, P-1 space group, a = 13.779(3) (?), b = 14.154(3) (?), c = 14.472(3) (?),α= 63.838(3)°,β= 86.871(3)°,γ= 65.200(3)°, V = 2270.1(7) (?), Z = 1, R1 = 0.0594, wR2 = 0.1613. It shows a 1-D infinite chain constructed from [BW12O40]5- polyoxoanions and trinuclear{[Cuâ… (2,2'-bipy)(4,4'-bipy)0.5]2}2+ cations by means of alternating fashion.4.{[Cuâ… (4, 4'-bipy)]3H2(α-BW12O40)}·3.5H2O: size 0.17×0.12×0.09 mm, triclinic system, P-1 space group, a = 12.7043(7) (?). b = 13.6868(7) (?), c = 18.4722(10) (?),α= 89.7990(10)°,β= 86.3030(10)°,γ= 74.7280(10)°, V = 3091.8(3) (?), Z = 2, R1 = 0.0337, wR2 = 0.0883. There are two types of-Cu-bipy- linear chains in the compound, and unprecedented 2-D extended structure built by [BW12O40]5- polyoxoanions and -Cuâ… -4.4'-bipy- linear chains are formed.5.|Cu(en)2(H2O)(2, 2'-bipy)]2H3BW12O40·2.5H2O: size 0.16×0.10×0.10 mm,monoclinic system. P2(1)/c space group, a = 19.511(2) (?), b = 12.2976(12) (?), c =25.059(3) (?),α= 90.00°,β= 91.266(2),γ= 90.00°, V= 6011.1(11) (?), Z = 4, R1 =0.0514, wR2 =0.1191. Via theÏ€-Ï€stacking interactions, hydrogenolysis, and staticinteractions, compound 5 construct a 3-D supramolecule structure.â…¡. Using polyoxometalate precursor, we have synthesized two organic-inorganic hybrids based on Keggin phosphortungstates:6.[Cu(en)2(H2O)][Cu5(en)10(PW12 O40)2]·4.75H2O: size 0.18×0.12×0.09 mm.(?)clinic system, P(?)space group, a = 12.6625(10) (?), b = 21.4545(19) (?), c = 22.393(2) (?),α= 90.00°,β= 84.0670(10)°,γ= 90.00°, V = 6050.9(9) (?), Z = 2, R1= 0.0892, wR2 =0.2449. A 2-D layer structure was constructured based on [PW12O40]3- building units by shairing {CUN2O2} octahedran and {Na3O14} clusters.7.[Ni(phen)3]2H5[Ni4(H2O)2(B-α-PW9O34)2Na]·1.5H2O: size 0.11×0.11×0.10 mm, orthorhombic system. Pbca space group, a = 21.2977(17) (?), b = 18.0949(14) (?), c = 31.724(2) (?),β= 90.00°, V= 12225.8(16) (?), Z = 4, R1 = 0.00339, wR2 = 0.0811. Compound 7 displays symmetrical sandwich-type polyanion framework based on [B-α-PW9O34]10- building blocks, in which the units linked each other forming a 2-D layer via Na+ ions.â…¢. We obtained a novel organic-inorganic hybrid based on paradodecatungstate anions:8.[Cu(en)2Na6(H2O)20(H4W12O42)]·16H2O: size 0.23×0.17×0.14 mm. triclinic system, P-1 space group, a = 11.8320(5) (?), b = 12.9601(6) (?), c = 14.1690(6) (?),α= 63.3480(10)°,β= 82.8440(10)°,γ= 68.9070(10)°, V = 1809.99(14) (?), Z = 1. R1 = 0.0247, wR2 = 0.0582. The results of the single crystal X-ray diffraction analyses show that compound 8 present a 2-D layer structureThe compounds were charactrized by IR, UV, XPS, XRD, single crystal X-ray structural analysis, and studied by TGA, fluorescence properties.
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