Making one VIV substitution for Mo on classical [Mo V2O4]2+ group: the first heterobimetallic Mo–V subunit in polyoxomolybdate–bisphosphonate family

Abstract

The development of a library of basic building units with distinct compositional and structural characteristics for the preparation of polyoxometalates remains a challenging and attractive endeavor. Herein, the first molybdovanadate cluster (1) modified by bisphosphonate (BP) ligands in a new [Mo^VV^IVO₄] building unit is successfully synthesized based on one V substituting for one Mo in the classical [Mo^V₂O₄] building unit. To compare the catalytic oxidation activity of the V-doped molybdovanadate cluster to that of other molybdovanadate clusters without VO in an organic model reaction, a molybdovanadate cluster (2) free of VO was prepared and using the atomically precise 1 and 2 as catalysts confirms the significance of the V-replaced model containing VO. This work provides an insight into the assembly and catalytic activity site design of Mo–V clusters and enriches the basic building units of the polyoxomolybdate (POMos)–BP family.