期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 17, 页码 5532-5550出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201807247
关键词
electron transfer; fragmentations; photoredox catalysis; radical anions; reductants; upconversion
资金
- National Science Foundation [CHE-1800329]
- Russian Science Foundation [17-73-20281]
- Russian Science Foundation [17-73-20281] Funding Source: Russian Science Foundation
The many applications of photon upconversion-conversion of low-energy photons into high-energy photons-raises the question of the possibility of electron upconversion. In this Review, we illustrate how the reduction potential can be increased by using the free energy of exergonic chemical reactions. Electron (reductant) upconversion can produce up to 20-25 kcal mol(-1) of additional redox potential, thus creating powerful reductants under mild conditions. We will present the two common types of electron-upconverting systems-dissociative (based on unimolecular fragmentations) and associative (based on the bimolecular formation of three-electron bonds). The possible utility of reductant upconversion encompasses redox chain reactions in electrocatalytic processes, photoredox cascades, design of peroxide-based medicines, firefly luminescence, and reductive repair of DNA photo-damage.
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