Controlled Reactivity Tuning of Metal-Functionalized Vanadium Oxide Clusters

Controlling the assembly and functionalization of molecular metal oxides [MxOy]n− (M=Mo, W, V) allows the targeted design of functional molecular materials. While general methods exist that enable the predetermined functionalization of tungstates and molybdates, no such routes are available for molecular vanadium oxides. Controlled design of polyoxovanadates, however, would provide highly active materials for energy conversion, (photo‐) catalysis, molecular magnetism, and materials science. To this end, a new approach has been developed that allows the reactivity tuning of vanadium oxide clusters by selective metal functionalization. Organic, hydrogen‐bonding cations, for example, dimethylammonium are used as molecular placeholders to block metal binding sites within vanadate cluster shells. Stepwise replacement of the placeholder cations with reactive metal cations gives mono‐ and difunctionalized clusters. Initial reactivity studies illustrate the tunability of the magnetic, redox, and catalytic activity. Stepwise functionalization of a vanadium oxide cluster by one or two functional metal centers is achieved by using a molecular placeholder approach. The novel strategy provides access to redox‐, catalytically, and magnetically active molecular materials.