Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer

Lateral charge transport in a redox-active monolayer can be utilized for solar energy harvesting. A model porphyrin system was chosen to study the influence of the solvent on lateral hole hopping, which plays a crucial role in the charge-transfer kinetics. We examined the influence of water, acetonitrile, and propylene carbonate as solvents. Hole-hopping lifetimes varied by nearly 3 orders of magnitude among solvents, ranging from 3 ns in water to 2800 ns in propylene carbonate, and increased nonlinearly as a function of added acetonitrile in aqueous solvent mixtures. These results elucidate the important roles of solvation, molecular packing dynamics, and lateral charge-transfer mechanisms that have implications for all dye-sensitized photoelectrochemical device designs.