Implications of Charge and Heteroatom Dopants on the Thermodynamics and Kinetics of Redox Reactions in Keggin-Type Polyoxometalates.

The utilization of polyoxometalate-based materials is largely dictated by their redox properties. Detailed understanding of the thermodynamic and kinetic efficiency of charge transfer is therefore essential to the development of polyoxometalate-based systems for target applications. Toward this end, we report electrochemical studies of a series of heteroatom-doped Keggin-type polyoxotungstate clusters [PWO] ( ), [VWO] ( ), [P(VW)O] ( ), and [V(VW)O] ( ) to elucidate the role of the identity and spatial location of heteroatoms and overall cluster charge on the rate constants of electron transfer and redox reaction entropies.