Making one VIV substitution for Mo on classical [Mo2VO4]2+ group: the first heterobimetallic Mo-V subunit in polyoxomolybdate-bisphosphonate family

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 [(MoVO4)-V-V-O-IV] building unit is successfully synthesized based on one V substituting for one Mo in the classical [(Mo2O4)-O-V] building unit. To compare the catalytic oxidation activity of the V-doped molybdovanadate cluster to that of other molybdovanadate clusters without V=O in an organic model reaction, a molybdovanadate cluster (2) free of V=O was prepared and using the atomically precise 1 and 2 as catalysts confirms the significance of the V-replaced model containing V=O. 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.

Automated summary

In this study, a new molybdovanadate cluster modified by bisphosphonate (BP) ligands was successfully synthesized, providing a new basic building unit for the preparation of polyoxometalates. By comparing the catalytic activity of the V-doped molybdovanadate cluster with other clusters without V=O in an organic model reaction, the significance of the V-replaced model containing V=O was confirmed.