| In this paper, using Keggin or polyoxoanions, transition metal ions and organic ligands as building blocks, eight kinds of novel polyoxometalate-based organic-inorganic hybrid compounds have been synthesized. They have been structurally characterized by elemental analyses, IR, TG and X-ray single crystal diffractions. The major results are as follows:1. Using Keggin-type polyoxoanions [PMo11VO40]4-,[SiW12O40]4-,[GeW12O40]4- and [PW11VO40]4- as template agents, four metal-oxides-based organic-inorganic hybrid framework compounds have been synthesized. [Mo2V2O9(bpy)6][PMo11VO40] (1) [Mo2V2O9(bpy)6][SiW12O40] (2) [Mo2V2O9(bpy)6][GeW12O40] (3) [Mo2V2O9(bpy)6][PW11VO40] (4)The four compounds are isomorphic. They are all based on Keggin anions as a template compounds. The host framework consists of heterometal-oxide of the Mo and V with theV-O-Mo-O-Mo-O-V arrangement and exhibits a finite 1D Z-shaped chain.2. Usingβ-Anderson-type polyoxoanions{Cr(OH)6Mo6O18}3- as building blocks, one Ag(I) coordination polymer has been synthesized at room temperature. Three (Mn(II), Ni(II), Co(II) coordination polymers have been synthesized hydrothermally by introducing 4,4'-bpy ligand. [{Ag(C6H5NO2)2}2][Ag{Cr(OH)6Mo6O18}(H2O)2](C6H5NO2)2 (5) (NH4)4[Mn{Cr(OH)6Mo6O18}2](4,4'-bpy)2 (6) NH4[Ni{Cr(OH)6Mo6O18}(H2O)2](4,4'-bpy)·4H2O (7) NH4[Co{Cr(OH)6Mo6O18}(H2O)2](4,4'-bpy)·4H2O (8)The host frameworks of the four compounds are all constructed byβ-Anderson-type polyoxoanions{Cr(OH)6Mo6O18}3- and transition metal ions. Compound 5 has two kinds of crystallographic independent Ag atoms (Ag1 and Ag2). Ag1 was linked with {Cr(OH)6Mo6O18}3- forming a 1D chain-like structure. Ag2 was linked with isonicotinic acid forming a {Ag2}2+cluster. In compound 6, Mn(II) exhibits hexa-coordination environment and is coordinated by six O atoms from four {Cr(OH)6Mo6O18}3- anions showing an infinite 1D zonal chain. Compounds 7 and 8 are isomorphic and exhibit a 2D layered structure via Ni2+/Co2+ linked with {Cr(OH)6Mo6O18}3- anions. |
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