Vibration-mediated long-wavelength photolysis of electronegative bonds beyond S0-S1 and S0-T1 transitions.
Commun Chem
; 7(1): 126, 2024 Jun 04.
Article
in En
| MEDLINE
| ID: mdl-38834838
ABSTRACT
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 S0-Sn or S0-Tn transitions. Here we report the photoinduced homolysis of electronegative interelement bonds using light at wavelengths much longer than theoretically and spectroscopically predicted for the S0-Sn or S0-Tn 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.
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Language:
En
Journal:
Commun Chem
Year:
2024
Document type:
Article
Affiliation country:
Japón
Country of publication:
Reino Unido