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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Published inAngewandte Chemie International Edition Vol. 58; no. 17; pp. 5532 - 5550
Main Authors Syroeshkin, Mikhail A., Kuriakose, Febin, Saverina, Evgeniya A., Timofeeva, Vladislava A., Egorov, Mikhail P., Alabugin, Igor V.
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 16.04.2019
Wiley-VCH Verlag
EditionInternational ed. in 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
fragmentations
upconversion
photoredox catalysis
reductants
electron transfer
radical anions
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Abstract 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).
AbstractList 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 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.
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.
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).
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.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.
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.
Author Alabugin, Igor V.
Syroeshkin, Mikhail A.
Kuriakose, Febin
Egorov, Mikhail P.
Saverina, Evgeniya A.
Timofeeva, Vladislava A.
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  fullname: Kuriakose, Febin
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  givenname: Vladislava A.
  surname: Timofeeva
  fullname: Timofeeva, Vladislava A.
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  givenname: Mikhail P.
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  surname: Alabugin
  fullname: Alabugin, Igor V.
  email: alabugin@chem.fsu.edu
  organization: Florida State University
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2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Issue 17
Keywords fragmentations
upconversion
photoredox catalysis
reductants
electron transfer
radical anions
Language English
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PublicationDate April 16, 2019
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PublicationDate_xml – month: 04
  year: 2019
  text: April 16, 2019
  day: 16
PublicationDecade 2010
PublicationPlace Germany
PublicationPlace_xml – name: Germany
– name: Weinheim
PublicationTitle Angewandte Chemie International Edition
PublicationTitleAlternate Angew Chem Int Ed Engl
PublicationYear 2019
Publisher Wiley Subscription Services, Inc
Wiley-VCH Verlag
Publisher_xml – name: Wiley Subscription Services, Inc
– name: Wiley-VCH Verlag
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Snippet The many applications of photon upconversion—conversion of low‐energy photons into high‐energy photons—raises the question of the possibility of “electron...
The many applications of photon upconversion-conversion of low-energy photons into high-energy photons-raises the question of the possibility of "electron...
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SubjectTerms 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
Title Upconversion of Reductants
URI https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fanie.201807247
https://www.ncbi.nlm.nih.gov/pubmed/30063285
https://www.proquest.com/docview/2205243584
https://www.proquest.com/docview/2080839000
https://univ-rennes.hal.science/hal-02090017
Volume 58
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