Inverted Region in Bimolecular Electron Transfer in Solution Enabled by Delocalization

Rate constants for bimolecular electron transfer (ET) increased with driving force, -ΔG°, reached a plateau, and then decreased in an inverted region. This rate data was described well by electron transfer theory subject to a diffusion-controlled limit. These were for ET from radical anions of polydecylthiophene (P3DT) to a series of acceptors in THF solution. When the donor was the smaller anion of quaterthiophene (T₄^•-) the inverted region was much less prominent and still less so for when the donor was the anion of bithiophene (T₂^•-). Description of the data using ET theory identifies smaller electronic couplings for the highly delocalized P3DT anions as enabling the inverted behavior: The presence of a Marcus inverted region is a consequence of delocalized electronic states. The results further imply that electronic couplings smaller than usually found for molecules in contact could boost efficiency of energy storage by electron transfer and identifies size-mismatch as an important concept in control of electronic couplings.