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Symmetry Effects in Photoinduced Electron Transfer in Chlorin‐Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region
In donor–acceptor dyads undergoing photoinduced electron transfer (PET), a direction or pathway for electron movement is usually dictated by the redox properties and the separation distance between the donor and acceptor subunits, while the effect of symmetry is less recognized. We have designed and...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7839475/ https://www.ncbi.nlm.nih.gov/pubmed/32628802 http://dx.doi.org/10.1002/chem.202002736 |
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author | Abel, Yvonne Vlassiouk, Ivan Lork, Enno Smirnov, Sergei Talipov, Marat R. Montforts, Franz‐Peter |
author_facet | Abel, Yvonne Vlassiouk, Ivan Lork, Enno Smirnov, Sergei Talipov, Marat R. Montforts, Franz‐Peter |
author_sort | Abel, Yvonne |
collection | PubMed |
description | In donor–acceptor dyads undergoing photoinduced electron transfer (PET), a direction or pathway for electron movement is usually dictated by the redox properties and the separation distance between the donor and acceptor subunits, while the effect of symmetry is less recognized. We have designed and synthesized two isomeric donor–acceptor assemblies in which electronic coupling between donor and acceptor is altered by the orbital symmetry control with the reorganization energy and charge transfer exothermicity being kept unchanged. Analysis of the optical absorption and luminescence spectra, supported by the DFT and TD‐DFT calculations, showed that PET in these assemblies corresponds to the Marcus inverted region (MIR) and has larger rate for isomer with weaker electronic coupling. This surprising observation provides the first experimental evidence for theoretically predicted adiabatic suppression of PET in MIR, which unambiguously controlled solely by symmetry. |
format | Online Article Text |
id | pubmed-7839475 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-78394752021-02-01 Symmetry Effects in Photoinduced Electron Transfer in Chlorin‐Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region Abel, Yvonne Vlassiouk, Ivan Lork, Enno Smirnov, Sergei Talipov, Marat R. Montforts, Franz‐Peter Chemistry Full Papers In donor–acceptor dyads undergoing photoinduced electron transfer (PET), a direction or pathway for electron movement is usually dictated by the redox properties and the separation distance between the donor and acceptor subunits, while the effect of symmetry is less recognized. We have designed and synthesized two isomeric donor–acceptor assemblies in which electronic coupling between donor and acceptor is altered by the orbital symmetry control with the reorganization energy and charge transfer exothermicity being kept unchanged. Analysis of the optical absorption and luminescence spectra, supported by the DFT and TD‐DFT calculations, showed that PET in these assemblies corresponds to the Marcus inverted region (MIR) and has larger rate for isomer with weaker electronic coupling. This surprising observation provides the first experimental evidence for theoretically predicted adiabatic suppression of PET in MIR, which unambiguously controlled solely by symmetry. John Wiley and Sons Inc. 2020-11-19 2020-12-18 /pmc/articles/PMC7839475/ /pubmed/32628802 http://dx.doi.org/10.1002/chem.202002736 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made. |
spellingShingle | Full Papers Abel, Yvonne Vlassiouk, Ivan Lork, Enno Smirnov, Sergei Talipov, Marat R. Montforts, Franz‐Peter Symmetry Effects in Photoinduced Electron Transfer in Chlorin‐Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region |
title | Symmetry Effects in Photoinduced Electron Transfer in Chlorin‐Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region |
title_full | Symmetry Effects in Photoinduced Electron Transfer in Chlorin‐Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region |
title_fullStr | Symmetry Effects in Photoinduced Electron Transfer in Chlorin‐Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region |
title_full_unstemmed | Symmetry Effects in Photoinduced Electron Transfer in Chlorin‐Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region |
title_short | Symmetry Effects in Photoinduced Electron Transfer in Chlorin‐Quinone Dyads: Adiabatic Suppression in the Marcus Inverted Region |
title_sort | symmetry effects in photoinduced electron transfer in chlorin‐quinone dyads: adiabatic suppression in the marcus inverted region |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7839475/ https://www.ncbi.nlm.nih.gov/pubmed/32628802 http://dx.doi.org/10.1002/chem.202002736 |
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