Barrier-Lowering Effects of Baird Antiaromaticity in Photoinduced Proton-Coupled Electron Transfer (PCET) Reactions.
J Am Chem Soc
; 143(43): 17970-17974, 2021 11 03.
Article
en En
| MEDLINE
| ID: mdl-34672631
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.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Asunto principal:
Piridinas
/
Agua
/
Fenol
/
Electrones
Idioma:
En
Revista:
J Am Chem Soc
Año:
2021
Tipo del documento:
Article
País de afiliación:
Estados Unidos
Pais de publicación:
Estados Unidos