Dark catalytic electron transfer in solid-state hydrogen-bonded electron-donor–electron-acceptor complexes

Abstract

The mechanism for the catalysis of electron-transfer reactions in systems with weak donor–acceptor properties has been considered. According to this mechanism, the reaction proceeds via the low-lying excited states of the complexes. These states are generated as a result of multiorbital bonds between the molecules of the reagents. The significant part played by hydrogen and other bridge bonds in the stabilization of the excited levels of the complexes is shown. The energetic characteristics of complexation (charge-transfer energy) and hydrogen-atom transfer (activation energy and reaction heat) are compared, taking as an example solid-phase hydrogen-bonded π complexes.