摘要
Four Keggin-based compounds, [CuI2(bmtm)3]2路[CuI2(bmtm)4]路(PW12O40)2 (trong class="boldFont">1trong>), (bmtm = 1,1鈥?bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)methane), [CuI3(bmte)3(PW12O40)] (trong class="boldFont">2trong>) (bmte = 1,2-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)ethane), [CuII(bmtb)3(HPW12O40)] (trong class="boldFont">3trong>) and [CuII(bmtb)3(HPMo12O40)] (trong class="boldFont">4trong>) (bmtb = 1,4-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)butane), have been designed and synthesized under hydrothermal conditions. By tuning the bis(tetrazole)-functionalized thioether ligands, compounds trong class="boldFont">1trong>-trong class="boldFont">4trong> exhibit Keggin-based bi-, tri- and mono-nuclear structures respectively, in which copper ion is +I oxidation state in compounds trong class="boldFont">1trong>-trong class="boldFont">2trong>, and +II oxidation state in compounds trong class="boldFont">3trong>-trong class="boldFont">4trong>. Compound trong class="boldFont">1trong> is composed of three moieties, [PW12O40]3鈭?/sup> anion and two kinds of bi-nuclear subunits [CuI2(bmtm)3]2+ and [CuI2(bmtm)4]2+. There exist abundant hydrogen-bonding and aryl stacking interactions inducing a two-dimensional (2D) supramolecular network of compound trong class="boldFont">1trong>. Compound trong class="boldFont">2trong> exhibits a tri-nuclear cluster [CuI3(bmte)3]3+, which is connected by [PW12O40]3鈭?/sup> anions to construct a 1D chain. Compounds trong class="boldFont">3trong> and trong class="boldFont">4trong> are isostructural, and show 2D layer structures, which are constructed from Keggin anions and mono-nuclear [CuII(bmtb)3]2+. In this 2D layer, the Keggin anions act as bidentate linkages to connect the CuII-btmb chains. The oxidation states of copper ions show great influence on the mono- and multi-nuclear structures of this series. In addition, the electrochemical properties of the title compounds have been investigated.