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

Two Keggin polyoxoanion-based hybrid compounds composed of Cu^I/tbz segments Cu^I₂(tbz)₂]Cu^I(tbz)₂(PMo^VI₁₀Mo₂^VO₄₀Cu^I₂)] (1) and Cu^I₂(tbz)₃]Cu^I (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 {Cu^I(tbz)₂(PMo^VI₁₀Mo₂^VO₄₀Cu^I₂)}^2 ?_n chain via hydrogen bonding and π–π interactions, in which {Cu^I₂(tbz)₂}^2 + segments are incorporated. Compound 2 is composed of one discrete PW₁₂ polyoxoanion, one {Cu^I(tbz)₂}⁺ segment and one {Cu^I₂(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.