Syntheses, Structures And Characterizations Of Polyoxometalates Modified By Metal Organic Complexes

Four polyoxometalates modified by metal organic complexes were successfully synthesized under hydrothermal conditions based on the classic type polyoxometalate building blocks, by exploiting appropriate transition metal cations and organic ligands. These complexes have been investigated by ICP-AES, CHN, IR, TG-DSC,CV and X-ray diffractometer analyses. The study on the synthetic conditions and rules for these new compounds and the exploration of relationship between structures and properties of these compounds were carried out.1. Two new organic-inorganic hybrid compounds have been hydrothermally synthesized by virtue transition metal ion Cu2+and organic ligand 2,2'-bipyridyl-3,3'-dicarboxylic acid (H2bpdc) based on the phosphorus-tunstate/phosphorus-molybdate:{[Cu4(H2O)5(H2bpdc) (Hbpdc)(bpdc)2][PW12O40]}·9H2O (1){[Cu4(H2O)5(H2bpdc) (Hbpdc)(bpdc)2][PMo12O40]}·8H2O (2)Compounds 1 and 2 were synthesized under identical conditions, except for choosing different polyoxometalate, which induce different packing modes. In compound 1, the adjacent double one-dimensional chains are linked via hydrogen bonding interactions to form a 2D structure. In compound 2, the 2D porous structure is formed via Cu-0 bonding to linking the double chains.2. A mixed-valence supramolecular compound was synthesized in situ reaction under hydrothermal condition[CuⅠ(2,2'-bipy)2]{[CuⅡ(2,2'-bipy)2]2(BW12O40)}-4H2O (3)The supramolecular compound constructed from bisupporting Keggin polyoxoanion cluster, [CuⅠ(2,2'-bipy)2]+coordination polymer fragments and H2O moleculars throughπ-πstacking and hydrogen bonding interactions.3. Using (NH4) 6Mo7O24·4H2O, CuSO4·5H2O, diphenyl and ethylenediamine as starting material, a 1-D chain-type supramolecular compound have been synthesized{(C2H10N2)[Mo3O10]}n (4)...