Angewandte Chemie - International Edition p. 6847 - 6852 (2020)
Update date:2022-08-11
Topics:
Kuribara, Takahito
Matsumoto, Koki
Muranaka, Atsuya
Nagasawa, Sho
Nakajima, Masaya
Nemoto, Tetsuhiro
Uchiyama, Masanobu
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.
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