Tian Ai-xiang, Yang Yang, Ying Jun, Li Na, Lin Xiao-ling, Zhang Ju-wen, Wang Xiu-li
Department of Chemistry, Bohai University, Jinzhou, 121000, P. R. China.
Dalton Trans. 2014 Jun 14;43(22):8405-13. doi: 10.1039/c4dt00107a.
Through using two kinds of bis(pyrazolyl) ligands, four polyoxometalate (POM)-based compounds were hydrothermally synthesized and structurally characterized, [Ag3(Hbhpe)2(H2O)(H2PMo12O40)]·H2O (1), [Ag(H2bdpm)2(H2PW12O40)]·4H2O (2), [Ag6(H2bdpm)6(HPW(VI)8W(V)4O40)]·2H2O (2) and [Ag4(H2bdpm)4(H2P2W18O62)]·3H2O (4) (H2bhpe = 1,2-bis(1-H-pyrazolate)ethane, H2bdpm = 1,1'-bis(3,5-dimethyl-1H-pyrazolate)methane). In compound 1, the Ag-Hbhpe subunit is a 2D layer containing large penta-membered cycles and small tri-nuclear Ag(I) clusters. The Keggin anions covalently float on the large cycles. In compound 2, the Keggin anions are fused by Ag(H2bdpm)2 subunits to form a 1D chain. Compound contains hexa-membered metal-organic cycles, which are further linked by Keggin anions to build a 1D chain. Adjacent chains share the Ag(I) ions to construct a 3D framework of 3. Compound 4 exhibits a wavy double-track chain structure, with the Wells-Dawson anions covalently suspended up and down this chain. The steric hindrance of -CH3 groups in H2bdpm leads to the formation of mono-nuclear Ag(I) subunits in 2 - 4. The influence of -CH3 steric hindrance in bis(pyrazolyl) ligands on the structures of 1 - 4 is discussed. The electrochemical and photocatalytic properties of the title compounds have been studied.
通过使用两种双（吡唑基）配体，水热合成并表征了四种基于多金属氧酸盐（POM）的化合物，[Ag3(Hbhpe)2(H2O)(H2PMo12O40)]·H2O (1)、[Ag(H2bdpm)2(H2PW12O40)]·4H2O (2)、[Ag6(H2bdpm)6(HPW(VI)8W(V)4O40)]·2H2O (2) 和 [Ag4(H2bdpm)4(H2P2W18O62)]·3H2O (4)（H2bhpe = 1,2 - 双（1 - H - 吡唑基）乙烷，H2bdpm = 1,1' - 双（3,5 - 二甲基 - 1H - 吡唑基）甲烷）。在化合物1中，Ag - Hbhpe亚基是一个包含大的五元环和小的三核Ag(I)簇的二维层。Keggin阴离子共价漂浮在大环上。在化合物2中，Keggin阴离子通过Ag(H2bdpm)2亚基融合形成一维链。化合物包含六元金属有机环，这些环通过Keggin阴离子进一步连接形成一维链。相邻链共享Ag(I)离子以构建化合物3的三维框架。化合物4呈现出波浪状双轨链结构，Wells - Dawson阴离子共价地上下悬浮在该链上。H2bdpm中 - CH3基团的空间位阻导致在2 - 4中形成单核Ag(I)亚基。讨论了双（吡唑基）配体中 - CH3空间位阻对1 - 4结构的影响。研究了标题化合物的电化学和光催化性能。
