8-Co-Containing Polyoxomolybdate for CO Photoreduction Reaction.

An S-shaped 8-Co-containing polyoxomolydate (NH)CsH[Co{Co(OH)(HO)(VMoO)(VMoO)}]·60HO () was obtained by the one-pot reaction. Compound adopts a triple-sandwich configuration, comprising two equivalent asymmetric sandwich-type tri-Co-containing {Co(OH)(HO)(VMoO)(VMoO)} units and a di-Co core linker. In particular, the {VMoO} segment adopts a unique petal-like architecture and represents a previously unreported structural subunit in polyoxometalate chemistry, thereby expanding the structural diversity of the molybdovanadate family. This study provides the first systematic investigation of molybdovanadates as catalysts for light-driven CO reduction. This work not only enhances structural diversity of TM-substituted sandwich-type POMs but also exemplifies their potential for catalytic applications.