Abstract: | Two new polyoxometalate-templated supramolecular compounds, CuI4(bpmb)4]PMoVI11MoVO40] (1) and CuI4(bpmb)4SiW12O40] (2) (bpmb = 1,4-bis(pyrazol-1-ylmethyl)benzene), have been synthesized under hydrothermal conditions and characterized by routine methods. Structural analysis shows that in 1, there exist crown-like CuI4(bpmb)4] coordination macrocycles, and the Keggin polyanions PMo VI11MoVO40]4? (abbr. as PMo12), which direct the crown-like macrocycle to form a 3-D supramolecular framework. In 2, there exist unusual meso-helix chains, and these chains are mutually interlaced in a wave–trough pattern, but without intersection resulting in a multi-cavity layer, in which the SiW12O40]4? (abbr. as SiW12) clusters as guest molecules occupy the cavities of the layers. The distinct structural features of the two compounds suggest that Keggin polyanions should play a significant role in the process of assembly. Electrocatalytic properties of 1 and 2 were investigated. |