A pyrazole-substituted diiron dithiolate complex [Fez（p-pdt）（CO）5（3,5-Me2Pz）] （1, 3,5-MezPz = 3,5-dimethylpyrazole） was prepared as a biomimetic model for the active site of [FeFe]-hydrogenase by CO-substitution of aU-carbonyl complex [Fe2（μ-pdt）（CO）6] with 3,5-Me2Pz. The molecular structure was confirmed by MS, IR, 1H NMR, elemental analysis and single-crystal X-ray analysis. Complex 1 crystallizes in the triclinic system, space group PI with a = 9.108（7）, b = 9.743（8）, c = 11.192（9）A, a = 109.235（5）, fl = 101.914（9）, y = 96.605（6）. In CH3CN solution, reversible transformation between 1 and the acetonitrile-substituted species [Fe2（p-pdt）- （CO）5（NCCH3）] was detected by both IR and cyclic voltammetry （CV）. The electrochemical proton reduction catalyzed by 1 in the presence of acetic acid was also studied in CH2C12.
Two new coordination polymers, [Cd（N3）2（Baep）l/2]n （1） and [Cd2（N3）4（CH3OH）（Bapp）I/.2]n （2） （Baep = 1,4-bis（2-aminoethyl）piperazine, Bapp = 1,4-bis（3-aminopropyl）piperazine） were synthesized. The crystal of 1 is of monoclinic system, space group P21/c with a = 9.341（7）, b = 11.677（9）, c = 8.195（6） A, fl = 93.925（13）, V= 891.8（11） A3, Z= 4, μ（MoKa） = 2.42 mm-1, Mr = 280.58, Dc = 2.090 g/cm3, the final R = 0.0297 and wR = 0.0720. The crystal of 2 is of triclinic system, space group PI with a = 9.121（5）, b = 9.666（5）, c = 10.250（6） A, a = 72.91（2）, β= 77.10（2）, V = 73.95（2）°, V = 820.0（8）°, Z = 2,μ（MoKa） = 2.62 mm-1, Mr= 522.10, Dc = 2.114 g/cm3, the final R = 0.0251 and wR = 0.0632. Single-crystal X-ray diffraction studies reveal that 1 is a 3D structure based on a dinuclear unit {Cd2（N3）a（Baep）}, in which the Baep ligands formed in situ display two different bridging modes. Compound 2 also has a 3D structure based on a tetranuclear cluster {Cda（N3）8（CH3OH）2（Bapp）}, in which the azido anions exhibit four different bridging modes （μ-1,1, μ-1,3, μ-l,l,1 and μ-1,1,3）. The thermal stability and fluorescent property of 1 and 2 have also been investigated.
Solvothermal reaction of [WS4]2-with CuCN and trithiocyanuric acid（L1） in orga-nic solvents gave rise to a new W/Cu/S polymer with a 2D anionic network,namely [Et4N]2[WS4Cu3（C3N3S3H1.5）2]（1）.The anionic layer of 1 is constructed by the T-shaped {WS4Cu3} subunits as nodes and L1 as linkers and features a（4,4） topology.Both 1 and its isomorphous compound [Et4N]2[MoS4Cu3（C3N3S3H1.5）2]（2） have been fully characterized by X-ray crystal analysis,IR and microanalyses.Compounds 1 and 2 show optical transitions with band gaps of 2.17 and 1.84 eV,respectively.
