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Exploiting Potential Inversion for Photoinduced Multielectron Transfer and Accumulation of Redox Equivalents in a Molecular Heptad

Nomrowski, Julia and Wenger, Oliver S.. (2018) Exploiting Potential Inversion for Photoinduced Multielectron Transfer and Accumulation of Redox Equivalents in a Molecular Heptad. Journal of the American Chemical Society, 140 (16). pp. 5343-5346.

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Abstract

Photoinduced multielectron transfer and reversible accumulation of redox equivalents is accomplished in a fully integrated molecular heptad composed of four donors, two photosensitizers, and one acceptor. The second reduction of the dibenzo[1,2]dithiin acceptor occurs more easily than the first by 1.3 V, and this potential inversion facilitates the light-driven formation of a two-electron reduced state with a lifetime of 66 ns in deaerated CH3CN. The quantum yield for formation of this doubly charge-separated photoproduct is 0.5%. In acidic oxygen-free solution, the reduction product is a stable dithiol. Under steady-state photoirradiation, our heptad catalyzes the two-electron reduction of an aliphatic disulfide via thiolate-disulfide interchange. Exploitation of potential inversion for the reversible light-driven accumulation of redox equivalents in artificial systems is unprecedented and the use of such a charge-accumulated state for multielectron photoredox catalysis represents an important proof-of-concept.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Wenger)
UniBasel Contributors:Wenger, Oliver and Nomrowski, Julia
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:American Chemical Society
ISSN:0002-7863
e-ISSN:1520-5126
Note:Publication type according to Uni Basel Research Database: Journal article -- The final publication is available at American Chemical Society, see DOI link
Language:English
Identification Number:
Last Modified:11 Jun 2018 13:15
Deposited On:11 Jun 2018 13:15

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