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Induced photoelectron circular dichroism onto an achiral chromophore

An achiral chromophore can acquire a chiral spectroscopic signature when interacting with a chiral environment. This so-called induced chirality is documented in electronic or vibrational circular dichroism, which arises from the coupling between electric and magnetic transition dipoles. Here, we de...

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Autores principales: Rouquet, Etienne, Roy Chowdhury, Madhusree, Garcia, Gustavo A., Nahon, Laurent, Dupont, Jennifer, Lepère, Valéria, Le Barbu-Debus, Katia, Zehnacker, Anne
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10562374/
https://www.ncbi.nlm.nih.gov/pubmed/37813848
http://dx.doi.org/10.1038/s41467-023-42002-1
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author Rouquet, Etienne
Roy Chowdhury, Madhusree
Garcia, Gustavo A.
Nahon, Laurent
Dupont, Jennifer
Lepère, Valéria
Le Barbu-Debus, Katia
Zehnacker, Anne
author_facet Rouquet, Etienne
Roy Chowdhury, Madhusree
Garcia, Gustavo A.
Nahon, Laurent
Dupont, Jennifer
Lepère, Valéria
Le Barbu-Debus, Katia
Zehnacker, Anne
author_sort Rouquet, Etienne
collection PubMed
description An achiral chromophore can acquire a chiral spectroscopic signature when interacting with a chiral environment. This so-called induced chirality is documented in electronic or vibrational circular dichroism, which arises from the coupling between electric and magnetic transition dipoles. Here, we demonstrate that a chiroptical response is also induced within the electric dipole approximation by observing the asymmetric scattering of a photoelectron ejected from an achiral chromophore in interaction with a chiral host. In a phenol–methyloxirane complex, removing an electron from an achiral aromatic π orbital localised on the phenol moiety results in an intense and opposite photoelectron circular dichroism (PECD) for the two enantiomeric complexes with (R) and (S) methyloxirane, evidencing the long-range effect (~5 Å) of the scattering chiral potential. This induced chirality has important structural and analytical implications, discussed here in the context of growing interest in laser-based PECD, for in situ, real time enantiomer determination.
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spelling pubmed-105623742023-10-11 Induced photoelectron circular dichroism onto an achiral chromophore Rouquet, Etienne Roy Chowdhury, Madhusree Garcia, Gustavo A. Nahon, Laurent Dupont, Jennifer Lepère, Valéria Le Barbu-Debus, Katia Zehnacker, Anne Nat Commun Article An achiral chromophore can acquire a chiral spectroscopic signature when interacting with a chiral environment. This so-called induced chirality is documented in electronic or vibrational circular dichroism, which arises from the coupling between electric and magnetic transition dipoles. Here, we demonstrate that a chiroptical response is also induced within the electric dipole approximation by observing the asymmetric scattering of a photoelectron ejected from an achiral chromophore in interaction with a chiral host. In a phenol–methyloxirane complex, removing an electron from an achiral aromatic π orbital localised on the phenol moiety results in an intense and opposite photoelectron circular dichroism (PECD) for the two enantiomeric complexes with (R) and (S) methyloxirane, evidencing the long-range effect (~5 Å) of the scattering chiral potential. This induced chirality has important structural and analytical implications, discussed here in the context of growing interest in laser-based PECD, for in situ, real time enantiomer determination. Nature Publishing Group UK 2023-10-09 /pmc/articles/PMC10562374/ /pubmed/37813848 http://dx.doi.org/10.1038/s41467-023-42002-1 Text en © The Author(s) 2023 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Rouquet, Etienne
Roy Chowdhury, Madhusree
Garcia, Gustavo A.
Nahon, Laurent
Dupont, Jennifer
Lepère, Valéria
Le Barbu-Debus, Katia
Zehnacker, Anne
Induced photoelectron circular dichroism onto an achiral chromophore
title Induced photoelectron circular dichroism onto an achiral chromophore
title_full Induced photoelectron circular dichroism onto an achiral chromophore
title_fullStr Induced photoelectron circular dichroism onto an achiral chromophore
title_full_unstemmed Induced photoelectron circular dichroism onto an achiral chromophore
title_short Induced photoelectron circular dichroism onto an achiral chromophore
title_sort induced photoelectron circular dichroism onto an achiral chromophore
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10562374/
https://www.ncbi.nlm.nih.gov/pubmed/37813848
http://dx.doi.org/10.1038/s41467-023-42002-1
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