Exploiting Charge-Transfer States for Maximizing Intersystem Crossing Yields in Organic Photoredox Catalysts

A key feature of prominent transition-metal-containing photoredox catalysts (PCs) is high quantum yield access to long-lived excited states characterized by a change in spin multiplicity. For organic PCs, challenges emerge for promoting excited-state intersystem crossing (ISC), particularly when pot...

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Published in:Journal of the American Chemical Society 2018-04, Vol.140 (14), p.4778-4781
Main Authors: Sartor, Steven M, McCarthy, Blaine G, Pearson, Ryan M, Miyake, Garret M, Damrauer, Niels H
Format: Article
Language:English
Subjects:
Catalysis
Molecular Structure
Organometallic Compounds - chemistry
Oxidation-Reduction
Photochemical Processes
Quantum Theory
Transition Elements - chemistry
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cited_by cdi_FETCH-LOGICAL-a483t-931dd1812986bcfbb8e80de5f1dcdc8ff64919a43c16a2697d6f1284c5386c8d3
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container_issue 14
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container_title Journal of the American Chemical Society
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creator Sartor, Steven M
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Damrauer, Niels H
description A key feature of prominent transition-metal-containing photoredox catalysts (PCs) is high quantum yield access to long-lived excited states characterized by a change in spin multiplicity. For organic PCs, challenges emerge for promoting excited-state intersystem crossing (ISC), particularly when potent excited-state reductants are desired. Herein, we report a design exploiting orthogonal π-systems and an intermediate-energy charge-transfer excited state to maximize ISC yields (ΦISC) in a highly reducing (E 0* = −1.7 V vs SCE), visible-light-absorbing phenoxazine-based PC. Simple substitution of N-phenyl for N-naphthyl is shown to dramatically increase ΦISC from 0.11 to 0.91 without altering catalytically important properties, such as E 0*.
doi_str_mv 10.1021/jacs.8b01001
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source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
subjects Catalysis
Molecular Structure
Organometallic Compounds - chemistry
Oxidation-Reduction
Photochemical Processes
Quantum Theory
Transition Elements - chemistry
title Exploiting Charge-Transfer States for Maximizing Intersystem Crossing Yields in Organic Photoredox Catalysts
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