A Direct S 0 →T n Transition in the Photoreaction of Heavy‐Atom‐Containing Molecules

Autor: Sho Nagasawa, Masanobu Uchiyama, Takahito Kuribara, Atsuya Muranaka, Tetsuhiro Nemoto, Masaya Nakajima, Koki Matsumoto
Rok vydání: 2020
Předmět:
Zdroj: Angewandte Chemie International Edition. 59:6847-6852
ISSN: 1521-3773
1433-7851
Popis: According to the Grotthuss-Draper law, light must be absorbed by a substrate to initiate a photoreaction. There have been several reports, however, on the promotion of photoreactions using hypervalent iodine during irradiation with light from a non-absorbing region. This contradiction gave rise to a mystery regarding photoreactions involving hypervalent iodine. We demonstrated that the photoactivation of hypervalent iodine with light from the apparently non-absorbing region proceeds via a direct S0 →Tn transition, which has been considered a forbidden process. Spectroscopic, computational, and synthetic experimental results support this conclusion. Moreover, the photoactivation mode could be extended to monovalent iodine and bromine, as well as bismuth(III)-containing molecules, providing new possibilities for studying photoreactions that involve heavy-atom-containing molecules.
Databáze: OpenAIRE
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