Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study

[EN] The photoinduced cycloreversion of oxetanes has been thoroughly investigated in connection with the photorepair of the well-known DNA (6-4) photoproducts. In the present work, the direct photolysis of the two regioisomers arising from the irradiation of benzophenone (BP) and 1,3-dimethylthymine...

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Autores: Blasco-Brusola, Alejandro, Vayá Pérez, Ignacio|||0000-0003-1682-9342, Navarrete-Miguel, Miriam, Giussani, Angelo, Roca-Sanjuan, Daniel, Miranda Alonso, Miguel Ángel
Tipo de recurso: artículo
Fecha de publicación:2020
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/176989
Acceso en línea:https://riunet.upv.es/handle/10251/176989
Access Level:acceso abierto
Palabra clave:QUIMICA ORGANICA
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dc.title.none.fl_str_mv Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study
title Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study
spellingShingle Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study
Blasco-Brusola, Alejandro
QUIMICA ORGANICA
title_short Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study
title_full Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study
title_fullStr Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study
title_full_unstemmed Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study
title_sort Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational study
dc.creator.none.fl_str_mv Blasco-Brusola, Alejandro
Vayá Pérez, Ignacio|||0000-0003-1682-9342
Navarrete-Miguel, Miriam
Giussani, Angelo
Roca-Sanjuan, Daniel
Miranda Alonso, Miguel Ángel
author Blasco-Brusola, Alejandro
author_facet Blasco-Brusola, Alejandro
Vayá Pérez, Ignacio|||0000-0003-1682-9342
Navarrete-Miguel, Miriam
Giussani, Angelo
Roca-Sanjuan, Daniel
Miranda Alonso, Miguel Ángel
author_role author
author2 Vayá Pérez, Ignacio|||0000-0003-1682-9342
Navarrete-Miguel, Miriam
Giussani, Angelo
Roca-Sanjuan, Daniel
Miranda Alonso, Miguel Ángel
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Instituto Universitario Mixto de Tecnología Química
Departamento de Química
Escuela Técnica Superior de Ingeniería Industrial
Fundación BBVA
GENERALITAT VALENCIANA
AGENCIA ESTATAL DE INVESTIGACION
Ministerio de Economía y Empresa
Ministerio de Economía y Competitividad
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv QUIMICA ORGANICA
topic QUIMICA ORGANICA
description [EN] The photoinduced cycloreversion of oxetanes has been thoroughly investigated in connection with the photorepair of the well-known DNA (6-4) photoproducts. In the present work, the direct photolysis of the two regioisomers arising from the irradiation of benzophenone (BP) and 1,3-dimethylthymine (DMT), namely the head-to-head (HH-1) and head-to-tail (HT-1) oxetane adducts, has been investigated by combining ultrafast spectroscopy and theoretical multiconfigurational quantum chemistry analysis. Both the experimental and computational results agree with the involvement of an excited triplet exciplex(3)[BPMIDLINE HORIZONTAL ELLIPSISDMT]* for the photoinduced oxetane cleavage to generate(3)BP* and DMT through an adiabatic photochemical reaction. The experimental signature of(3)[BPMIDLINE HORIZONTAL ELLIPSISDMT]* is the appearance of an absorption band atca.400 nm, detected by femtosecond transient absorption spectroscopy. Its formation is markedly regioselective, as it is more efficient and proceeds faster for HH-1 (similar to 2.8 ps) than for HT-1 (similar to 6.3 ps). This is in line with the theoretical analysis, which predicts an energy barrier to reach the triplet exciplex for HT-1, in contrast with a less hindered profile for HH-1. Finally, the more favorable adiabatic cycloreversion of HH-1 compared to that of HT-1 is explained by its lower probability to reach the intersystem crossing with the ground state, which would induce a radiationless deactivation process leading either to a starting adduct or to a dissociated BP and DMT.
publishDate 2020
dc.date.none.fl_str_mv 2020
2020-09-21
dc.type.none.fl_str_mv journal 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://riunet.upv.es/handle/10251/176989
url https://riunet.upv.es/handle/10251/176989
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 http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016 CTQ2017-89416-R FUNCIONALIZACION DE NANOPARTICULAS DE ORO CON MARCADORES BIOLOGICOS Y SENSIBILIZADORES DE OXIGENO SINGLETE PARA SU USO EN BIOMEDICINA
Generalitat Valenciana https://doi.org/10.13039/501100003359 GRISOLIAP%2F2017%2F005 AYUDA SANTIAGO GRISOLIA PROYECTO: FOTOCATALISIS REDOX EN QUIMICA ORGANICA. ESTUDIOS MECANISTICOS BASADOS EN TECNICAS FOTOFISICAS CON RESOLUCION TEMPORAL.
Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 MDM-2015-0538 INSTITUTO DE CIENCIA MOLECULAR
Generalitat Valenciana https://doi.org/10.13039/501100003359 PROMETEO%2F2017%2F075 REACCIONES FOTOQUIMICAS DE BIOMOLECULAS.
Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 RYC-2015-17737 RYC-2015-17737
Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 RYC-2015-19234 RYC-2015-19234
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reserva de todos los derechos
http://rightsstatements.org/vocab/InC/1.0/
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
Reserva de todos los derechos
http://rightsstatements.org/vocab/InC/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv The Royal Society of Chemistry
publisher.none.fl_str_mv The Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
repository.name.fl_str_mv
repository.mail.fl_str_mv
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spelling Regiochemical memory in the adiabatic photolysis of thymine-derived oxetanes. A combined ultrafast spectroscopic and CASSCF/CASPT2 computational studyBlasco-Brusola, AlejandroVayá Pérez, Ignacio|||0000-0003-1682-9342Navarrete-Miguel, MiriamGiussani, AngeloRoca-Sanjuan, DanielMiranda Alonso, Miguel ÁngelQUIMICA ORGANICA[EN] The photoinduced cycloreversion of oxetanes has been thoroughly investigated in connection with the photorepair of the well-known DNA (6-4) photoproducts. In the present work, the direct photolysis of the two regioisomers arising from the irradiation of benzophenone (BP) and 1,3-dimethylthymine (DMT), namely the head-to-head (HH-1) and head-to-tail (HT-1) oxetane adducts, has been investigated by combining ultrafast spectroscopy and theoretical multiconfigurational quantum chemistry analysis. Both the experimental and computational results agree with the involvement of an excited triplet exciplex(3)[BPMIDLINE HORIZONTAL ELLIPSISDMT]* for the photoinduced oxetane cleavage to generate(3)BP* and DMT through an adiabatic photochemical reaction. The experimental signature of(3)[BPMIDLINE HORIZONTAL ELLIPSISDMT]* is the appearance of an absorption band atca.400 nm, detected by femtosecond transient absorption spectroscopy. Its formation is markedly regioselective, as it is more efficient and proceeds faster for HH-1 (similar to 2.8 ps) than for HT-1 (similar to 6.3 ps). This is in line with the theoretical analysis, which predicts an energy barrier to reach the triplet exciplex for HT-1, in contrast with a less hindered profile for HH-1. Finally, the more favorable adiabatic cycloreversion of HH-1 compared to that of HT-1 is explained by its lower probability to reach the intersystem crossing with the ground state, which would induce a radiationless deactivation process leading either to a starting adduct or to a dissociated BP and DMT.Financial support from the Spanish Government (RYC-2015-17737, CTQ2017-89416-R, RYC-2015-19234, CTQ2017-87054-C2-2-P, and MDM-2015-0538), from the Conselleria d'Educacio, Investigacio, Cultura i Esport (PROMETEO/2017/075 and GRISOLiAP/2017/005) and from the Universitat de Valencia (postdoctoral grant within the "Atraccio de Talent 2019" Program for A. G.) is gratefully acknowledged. This work was also supported by a 2019 Leonardo Grant for Researchers and Cultural Creators, BBVA Foundation. The Foundation takes no responsibility for the opinions, statements, and contents of this project, which are entirely the responsibility of its authors.The Royal Society of ChemistryInstituto Universitario Mixto de Tecnología QuímicaDepartamento de QuímicaEscuela Técnica Superior de Ingeniería IndustrialFundación BBVAGENERALITAT VALENCIANAAGENCIA ESTATAL DE INVESTIGACIONMinisterio de Economía y EmpresaMinisterio de Economía y CompetitividadRepositorio Institucional de la Universitat Politècnica de València Riunet20202020-09-21journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfapplication/pdfhttps://riunet.upv.es/handle/10251/176989reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016 CTQ2017-89416-R FUNCIONALIZACION DE NANOPARTICULAS DE ORO CON MARCADORES BIOLOGICOS Y SENSIBILIZADORES DE OXIGENO SINGLETE PARA SU USO EN BIOMEDICINAGeneralitat Valenciana https://doi.org/10.13039/501100003359 GRISOLIAP%2F2017%2F005 AYUDA SANTIAGO GRISOLIA PROYECTO: FOTOCATALISIS REDOX EN QUIMICA ORGANICA. ESTUDIOS MECANISTICOS BASADOS EN TECNICAS FOTOFISICAS CON RESOLUCION TEMPORAL.Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 MDM-2015-0538 INSTITUTO DE CIENCIA MOLECULARGeneralitat Valenciana https://doi.org/10.13039/501100003359 PROMETEO%2F2017%2F075 REACCIONES FOTOQUIMICAS DE BIOMOLECULAS.Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 RYC-2015-17737 RYC-2015-17737Ministerio de Economía y Competitividad http://dx.doi.org/10.13039/501100003329 RYC-2015-19234 RYC-2015-19234open accesshttp://purl.org/coar/access_right/c_abf2Reserva de todos los derechoshttp://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/1769892026-06-13T07:49:27Z
score 15,301603

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