Elucidation of Design Criteria for V-based Redox Mediators: Structure-Function Relationships that Dictate Rates of Heterogeneous Electron Transfer.

Redox mediators are attractive solutions for addressing the stringent kinetic stipulations required for efficient energy conversion processes. In this work, we compare the electrochemical properties of four vanadium complexes, namely [V(acac) 3 ], [V 6 O 7 (OMe) 12 ], [ n Bu 4 N] 3 [V 6 O 13 (TRIS NO2 ) 2 ], and [ n Bu 4 N] 5 [V 18 O 46 (NO 3 )] in non-aqueous solutions on glassy carbon electrodes. The goal of this study is to investigate the electron transfer kinetics and diffusivity of these compounds under identical experimental conditions to develop an understanding of structure-function relationships that dictate the physicochemical properties of vanadium oxide assemblies. Complex selection was dictated by two criteria - (1) nuclearity of the transition metal complexes (2) distribution of electron density in the native electronic configuration. Our analyses establish that electronic communication between metal centers significantly impacts charge transfer kinetics of these vanadium-based compounds.