Barrier-Lowering Effects of Baird Antiaromaticity in Photoinduced Proton-Coupled Electron Transfer (PCET) Reactions
Lucas J. Karas, Chia‐Hua Wu, Judy I. Wu
Abstract
Many popular organic chromophores that catalyze photoinduced proton-coupled electron transfer (PCET) reactions are aromatic in the ground state but become excited-state antiaromatic in the lowest ππ* state. We show that excited-state antiaromaticity makes electron transfer easier. Two representative photoinduced electron transfer processes are investigated: (1) the photolysis of phenol and (2) solar water splitting of a pyridine–water complex. In the selected reactions, the directions of electron transfer are opposite, but the net result is proton transfer following the direction of electron transfer. Nucleus-independent chemical shifts (NICS), ionization energies, electron affinities, and PCET energy profiles of selected [4n] and [4n + 2] π-systems are presented, and important mechanistic implications are discussed.