Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches

Simulations based on molecular dynamics coupled to excitation energy calculations were used to generate simulated absorption spectra for a family of halide derivatives of azobenzene, a family of photoswitch molecules with a weak absorption band around 400-600 nm and potential uses in living tissue....

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Autores: Gelabert, Ricard|||0000-0001-6506-5786, Moreno, Miquel|||0000-0002-2784-1307, Lluch, José M.|||0000-0002-7536-1869
Formato: artículo
Fecha de publicación:2023
País:España
Recursos:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:270670
Acesso em linha:https://ddd.uab.cat/record/270670
https://dx.doi.org/urn:doi:10.3390/ijms24010025
Access Level:acceso abierto
Palavra-chave:Photoswitch
Azobenzene derivatives
Mammal optical window
Absorption spectrum
Absorption band shape
Molecular dynamics simulations
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spelling Predicting the Electronic Absorption Band Shape of Azobenzene PhotoswitchesGelabert, Ricard|||0000-0001-6506-5786Moreno, Miquel|||0000-0002-2784-1307Lluch, José M.|||0000-0002-7536-1869PhotoswitchAzobenzene derivativesMammal optical windowAbsorption spectrumAbsorption band shapeMolecular dynamics simulationsSimulations based on molecular dynamics coupled to excitation energy calculations were used to generate simulated absorption spectra for a family of halide derivatives of azobenzene, a family of photoswitch molecules with a weak absorption band around 400-600 nm and potential uses in living tissue. This is a case where using the conventional approach in theoretical spectroscopy (estimation of absorption maxima based on the vertical transition from the potential energy minimum on the ground electronic state) does not provide valid results that explain how the observed band shape extends towards the low energy region of the spectrum. The method affords a reasonable description of the main features of the low-energy UV-Vis spectra of these compounds. A bathochromic trend was detected linked to the size of the halide atom. Analysis of the excitation reveals a correlation between the energy of the molecular orbital where excitation starts and the energy of the highest occupied atomic orbital of the free halide atom. This was put to the test with a new brominated compound with good results. The energy level of the highest occupied orbital on the free halide was identified as a key factor that strongly affects the energy gap in the photoswitch. This opens the way for the design of bathochromically shifted variants of the photoswitch with possible applications. 22023-01-0120232023-01-01Articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/270670https://dx.doi.org/urn:doi:10.3390/ijms24010025reponame:Dipòsit Digital de Documents de la UABinstname:Universitat Autònoma de BarcelonaInglésengAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 PID2020-113764GB-I00open accesshttp://purl.org/coar/access_right/c_abf2Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:2706702026-06-06T12:50:31Z
dc.title.none.fl_str_mv Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches
title Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches
spellingShingle Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches
Gelabert, Ricard|||0000-0001-6506-5786
Photoswitch
Azobenzene derivatives
Mammal optical window
Absorption spectrum
Absorption band shape
Molecular dynamics simulations
title_short Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches
title_full Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches
title_fullStr Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches
title_full_unstemmed Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches
title_sort Predicting the Electronic Absorption Band Shape of Azobenzene Photoswitches
dc.creator.none.fl_str_mv Gelabert, Ricard|||0000-0001-6506-5786
Moreno, Miquel|||0000-0002-2784-1307
Lluch, José M.|||0000-0002-7536-1869
author Gelabert, Ricard|||0000-0001-6506-5786
author_facet Gelabert, Ricard|||0000-0001-6506-5786
Moreno, Miquel|||0000-0002-2784-1307
Lluch, José M.|||0000-0002-7536-1869
author_role author
author2 Moreno, Miquel|||0000-0002-2784-1307
Lluch, José M.|||0000-0002-7536-1869
author2_role author
author
dc.subject.none.fl_str_mv Photoswitch
Azobenzene derivatives
Mammal optical window
Absorption spectrum
Absorption band shape
Molecular dynamics simulations
topic Photoswitch
Azobenzene derivatives
Mammal optical window
Absorption spectrum
Absorption band shape
Molecular dynamics simulations
description Simulations based on molecular dynamics coupled to excitation energy calculations were used to generate simulated absorption spectra for a family of halide derivatives of azobenzene, a family of photoswitch molecules with a weak absorption band around 400-600 nm and potential uses in living tissue. This is a case where using the conventional approach in theoretical spectroscopy (estimation of absorption maxima based on the vertical transition from the potential energy minimum on the ground electronic state) does not provide valid results that explain how the observed band shape extends towards the low energy region of the spectrum. The method affords a reasonable description of the main features of the low-energy UV-Vis spectra of these compounds. A bathochromic trend was detected linked to the size of the halide atom. Analysis of the excitation reveals a correlation between the energy of the molecular orbital where excitation starts and the energy of the highest occupied atomic orbital of the free halide atom. This was put to the test with a new brominated compound with good results. The energy level of the highest occupied orbital on the free halide was identified as a key factor that strongly affects the energy gap in the photoswitch. This opens the way for the design of bathochromically shifted variants of the photoswitch with possible applications.
publishDate 2023
dc.date.none.fl_str_mv 2
2023-01-01
2023
2023-01-01
dc.type.none.fl_str_mv Article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://ddd.uab.cat/record/270670
https://dx.doi.org/urn:doi:10.3390/ijms24010025
url https://ddd.uab.cat/record/270670
https://dx.doi.org/urn:doi:10.3390/ijms24010025
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 PID2020-113764GB-I00
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Dipòsit Digital de Documents de la UAB
instname:Universitat Autònoma de Barcelona
instname_str Universitat Autònoma de Barcelona
reponame_str Dipòsit Digital de Documents de la UAB
collection Dipòsit Digital de Documents de la UAB
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repository.mail.fl_str_mv
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