Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S 0 -S 1 and S 0 -T 1 transitions.

Autor: Araujo Dias AJ; Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan., Muranaka A; Molecular Structure Characterization Unit, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan., Uchiyama M; Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan., Tanaka K; Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan. tanaka.k.cg@m.titech.ac.jp., Nagashima Y; Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8550, Japan. nagashima.y.ae@m.titech.ac.jp.
Jazyk: angličtina
Zdroj: Communications chemistry [Commun Chem] 2024 Jun 04; Vol. 7 (1), pp. 126. Date of Electronic Publication: 2024 Jun 04.
DOI: 10.1038/s42004-024-01208-0
Abstrakt: Photolysis is an attractive method in organic synthesis to produce free radicals through direct bond cleavage. However, in this method, specific irradiation wavelengths of light have been considered indispensable for excitation through S 0 -S n or S 0 -T n transitions. Here we report the photoinduced homolysis of electronegative interelement bonds using light at wavelengths much longer than theoretically and spectroscopically predicted for the S 0 -S n or S 0 -T n transitions. This long-wavelength photolysis proceeds in N-Cl, N-F, and O-Cl bonds at room temperature under blue, green, and red LED irradiation, initiating diverse radical reactions. Through experimental, spectroscopic, and computational studies, we propose that this "hidden" absorption is accessible via electronic excitations from naturally occurring vibrationally excited ground states to unbonded excited states and is due to the electron-pair repulsion between electronegative atoms.
(© 2024. The Author(s).)
Databáze: MEDLINE
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