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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...

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Autores principales: Abel, Yvonne, Vlassiouk, Ivan, Lork, Enno, Smirnov, Sergei, Talipov, Marat R., Montforts, Franz‐Peter
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
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.
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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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