Two Keggin polyoxoanion-based hybrids composed of CuI/tbz segments: Syntheses, structures and electrochemical properties

Two Keggin polyoxoanion-based hybrid compounds composed of CuI/tbz segments [CuI2(tbz)2][CuI(tbz)2(PMoVI10Mo2VO40CuI2)] (1) and [CuI2(tbz)3][CuI (tbz)2](PW12O40) (2), have been hydrothermally synthesized. In compound 1, a 3D supramolecular framework with 2D channels is constructed from a novel cap-to-cap {CuI(tbz)2(PMoVI10Mo2VO40CuI2)}2 −n chain via hydrogen bonding and π–π interactions, in which {CuI2(tbz)2}2 + segments are incorporated. Compound 2 is composed of one discrete PW12 polyoxoanion, one {CuI(tbz)2}+ segment and one {CuI2(tbz)3}2 + segment, displaying a 3D supramolecular structure through hydrogen bonding and π–π interactions. The results indicate that the polyoxoanions and configurations of tbz ligand play the key roles in the self-assembly processes. The electrochemical properties of compounds 1 and 2 have been investigated.