The effect of inner-sphere reorganization on charge separated state lifetimes at sensitized TiO₂ interfaces

Improving the efficiency of photo-electrocatalytic cells depends on controlling the rates of interfacial electron transfer to promote the formation of long-lived charge separated states. Ultimately, for efficient catalytic assemblies to see widespread implementation, repeated electron transfer in the absence of charge recombination needs to be realized. In this study, a series of manganese-based transition metal complexes known to undergo charge transfer-induced spin crossover are employed to study how significant increases in inner-sphere reorganization energy affect the rates of interfacial electron transfer. Each complex is characterized by transient spectroscopic and electrochemical methods to calculate the rate of electron transfer to a model chromophore anchored to the surface of a TiO₂ film. Likewise, open-circuit voltage decay measurements were used to determine the voltage-dependent lifetime of injected electrons in TiO₂ in the presence of each complex. To further characterize the rates of electronic recombination, density functional theory was used to calculate the inner-sphere and outer-sphere reorganization energy for each complex. These calculations were then combined with classical Marcus theory to determine the theoretical rate of back-electron transfer from the TiO₂ conduction band. These results show that, in model complexes, a significant reduction in the recombination rate constant is achieved for complexes possessing a significant inner-sphere reorganization energy.