Higher activation barriers can lift exothermic rate restrictions in electron transfer and enable faster reactions.

Electron transfer reactions are arguably the simplest chemical reactions but they have not yet ceased to intrigue chemists. Charge-separation and charge-recombination reactions are at the core of life-sustaining processes, molecular electronics and solar cells. Intramolecular electron donor-acceptor systems capture the essential features of these reactions and enable their fundamental understanding. Here, we report intramolecular electron transfers covering a range of 100 kcal mol-1 in exothermicities that show an increase, then a decrease, and finally an increase in rates with the driving force of the reactions. Concomitantly, apparent activation energies change from positive, to negative and finally to positive. Reactions with positive activation energies are found to be faster than analogous reactions with negative effective activation energies. The increase of the reorganization energy with the driving force of the reactions can explain the peculiar free-energy relationship observed in this work.