| In this thesis, eight compounds based on saturated and monovacant Keggin polyoxoanion clusters as building blocks have been synthesized under hydrothermal and normal temperature conditions, and characterized by elemental analysis, IR, TG and X-ray single crystal diffraction. The photocatalytic H2 evolution and the electrochemistry have been studied for some of them.1. Four lanthanide complexes have been synthesized hydrothermally: H[{Ce(H2O)5}2{Ce(pdc)2(H2O)4}{Ce(pdc)3}(PW12O40)]·2H2O 1 {H[Ce(pdc)(H2O)6]2}[PMo12O40]·2H2O 2 {H[La(H2O)4(pdc)]4}[BW12O40]·2H2O 3 {H[Ce(H2O)4(pdc)]4}[BW12O40]·2H2O 4Complex 1 exhibits 2D layer structure constructed by Ce3+ and pdc ligands. The layers are pillared by Keggin anions. Complex 2 exhibits a 0D structure build from [PMo12O40]3- anions and [Ce(pdc)(H2O)6]2+ units. In complexes 3 and 4, a 3D organic framework is constructed by rare-earth ions and pdc and [BW12O40]5- are embedded in the organic framework. Electrochemistry and photocatalytic H2 evolution have been studied for complexe1. It is found that complexe 1 exhibits photocatalytic activity for H2 evolution at the rate of 3.4μmol h-1.2. One 1D Sm3+ complex has been synthesized using monovacant Keggin polyoxoanion clusters, organic solvent DMSO and rare-earth ions at 70℃and pH = 5.15: [Sm2(H2O)9(DMSO)]2(OH)2[Sm(H2O)3(DMSO)(SiW11O39)]2·19H2O 5In complex 5, a 1D chain-like structure is formed by Sm3+ and [SiW11O39]8-, then a 2D double chain-like structure is constructed by Sm(DMSO)(H2O) dimers and the 1D chain structure.3. Three Cu(â…¡/â… ) complexes have been hydrothermally synthesized using SiW12O404- anions, 4,4'-bipy and metal Cu2+ ions: {[Cu(4,4'-bipy)]2(HSiW12O40)}[Cu(4,4'-bipy)]·H2O 6 [Cu(4,4'-bipy)]2(H2SiW12O40) 7 [H2Cu2(4,4'-bipy)3(CH3COO)2](SiW12O40) 8In complex 6, one-dimensional cationic polymer chains, {Cu(4,4'-bipy)}+, link [SiW12O40]4- anions to form a 2D layer structure. In complex 7, a 1D rail-like structure is constructed from {Cu(4,4-bipy)}+ and [SiW12O40]4- anions. In complex 8, a 2D layer structure is constructed from [SiW12O40]4- and metal organic fragment, adjacent layers are further extended into 3D structure by hydrogen bonding interactions, the layer structure is arranged in a manner of an ABAB…mode along the c axis. Electrochemistry has been studied for complexe 6,7,8. |
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