Effect of the Keggin anions on assembly of CuI-bis(tetrazole) thioether complexes containing multinuclear CuI-cluster

In order to investigate the effect of polyoxometalate (POM) on the assembly of transition metal-bis(tetrazole) thioether complexes, three new complexes based on different Keggin anions and multinuclear CuI-cluster [CuI12(bmtr)9(HSiMo12O40)4] (1), [CuI3(bmtr)3(PM12O40)] (M=W for 2; Mo for 3) (bmtr=1,3-bis(1-methyl-5-mercapto-1,2,3,4-tetrazole)propane), have been hydrothermally synthesized and characterized by routine physical methods and single crystal X-ray diffraction. In compound 1, two kinds of nanometer-scale tetranuclear subunits linked by [SiMo12O40]4− polyanions assemble a (3, 4)-connected three-dimensional (3D) self-penetrating framework. Compounds 2 and 3 are isostructural, exhibiting a 1D chain with [PW12O40]3−/[PMo12O40]3− polyanions and trinuclear clusters arranging alternately. The distinct structural differences between these POM-based CuI-bmtr complexes of 1 and 2/3 maybe rest on the contrast of Keggin-type polyoxometalate with different central heteroatoms, which have been discussed in detail. In addition, the electrochemical properties of the title complexes have been investigated.

Three new complexes based on different Keggin anions and multinuclear CuI-cluster have been synthesized under hydrothermal conditions. The Keggin polyanions with different central heteroatoms play a key role.Figure optionsDownload as PowerPoint slideHighlights
► The flexible bis(tetrazole)-based thioether ligand with some advantages have been used.
► The effect of Keggin anions with different central heteroatoms has been discussed in detail.
► The electrochemical behaviors and electrocatalysis property have been investigated.