Upconversion of Reductants

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 reaction...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-04, Vol.58 (17), p.5532-5550
Main Authors: Syroeshkin, Mikhail A., Kuriakose, Febin, Saverina, Evgeniya A., Timofeeva, Vladislava A., Egorov, Mikhail P., Alabugin, Igor V.
Format: Article
Language:English
Subjects:
Cascades
Chemical reactions
Chemical Sciences
Deoxyribonucleic acid
DNA
DNA repair
electron transfer
Electrons
Fireflies
fragmentations
Free energy
Organic chemistry
Peroxide
Photons
photoredox catalysis
radical anions
Redox potential
reductants
Upconversion
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Summary: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 photodamage. Electrons and photons are essential chemical “currencies” that are commonly traded in chemical transformations. The many applications of photon upconversion raises the question of the possibility of “electron upconversion”. This Review describes the two common types of electron‐upconverting systems: dissociative (based on unimolecular fragmentations) and associative (based on the bimolecular formation of three‐electron bonds).
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201807247