Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry

The photoinduced cycloreversion of oxetane derivatives is of considerable biological interest since these compounds are involved in the photochemical formation and repair of the highly mutagenic pyrimidine (6-4) pyrimidone DNA photoproducts ((6-4)PPs). Previous reports have dealt with the photoreact...

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Autores: Blasco-Brusola, A., Tamarit, Lorena, Navarrete-Miguel, M., Roca-Sanjuán, Daniel, Miranda, M. A., Vayá, Ignacio
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2024
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/389110
Acesso em linha:http://hdl.handle.net/10261/389110
Access Level:Acceso aberto
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spelling Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistryBlasco-Brusola, A.Tamarit, LorenaNavarrete-Miguel, M.Roca-Sanjuán, DanielMiranda, M. A.Vayá, IgnacioThe photoinduced cycloreversion of oxetane derivatives is of considerable biological interest since these compounds are involved in the photochemical formation and repair of the highly mutagenic pyrimidine (6-4) pyrimidone DNA photoproducts ((6-4)PPs). Previous reports have dealt with the photoreactivity of heterodimeric oxetanes composed mainly of benzophenone (BP) and thymine (Thy) or uracil (Ura) derivatives. However, these models are far from the non-isolable Thy〈º〉Thy dimers, which are the real precursors of (6-4)PPs. Thus, we have synthesized two chemically stable homodimeric oxetanes through the Paternò-Büchi reaction between two identical enone units, i.e. 1,4-benzoquinone (BQ) and 1,4-naphthoquinone (NQ), that led to formation of BQ-Ox and NQ-Ox, respectively. Their photoreactivity has been studied by means of steady-state photolysis and transient absorption spectroscopy from the femtosecond to the microsecond time scale. Thus, photolysis of BQ-Ox and NQ-Ox led to formation of the monomeric BQ or NQ, respectively, through ring opening in a “non-adiabatic” process. Accordingly, the transient absorption spectra of the triplet excited quinones (BQ* and NQ*) were not observed as a result of direct photolysis of the quinone-derived oxetanes. In the case of NQ-Ox, a minor signal corresponding to NQ* was detected; its formation was ascribed to minor photodegradation of the oxetane during acquisitions of the spectra during the laser experiments. These results are supported by computational analyses based on density functional theory and multiconfigurational quantum chemistry (CASSCF/CASPT2); here, an accessible conical intersection between the ground and excited singlet states has been characterized as the main structure leading to deactivation of excited BQ-Ox or NQ-Ox. This behavior contrasts with those previously observed for heterodimeric thymine-derived oxetanes, where a certain degree of ring opening into the excited triplet state is observed.Grants PID2020-115010RB-I00 and PID2021-127199NB-I00 funded by MCIN/AEI/10.13039/501100011033 and grants from Conselleria d’Innovació, Universitats, Ciència i Societat Digital (CIAICO/2021/061, CIAICO/2022/121 and CIAPOS/2021/87) are gratefully acknowledged. M. N.-M. is thankful to the Universitat de València for her “Atracció de Talent 2020” predoctoral grant. The authors would like to thank the use of RIAIDT-USC analytical facilities for the X-ray crystallography analysis.Royal Society of Chemistry (UK)Ministerio de Ciencia e Innovación (España)Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2025202520242025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/389110reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-115010RB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127199NB-I00http://dx.doi.org/10.1039/d4cp00830hSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3891102026-05-22T06:33:51Z
dc.title.none.fl_str_mv Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry
title Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry
spellingShingle Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry
Blasco-Brusola, A.
title_short Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry
title_full Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry
title_fullStr Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry
title_full_unstemmed Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry
title_sort Photolytic splitting of homodimeric quinone-derived oxetanes studied by ultrafast transient absorption spectroscopy and quantum chemistry
dc.creator.none.fl_str_mv Blasco-Brusola, A.
Tamarit, Lorena
Navarrete-Miguel, M.
Roca-Sanjuán, Daniel
Miranda, M. A.
Vayá, Ignacio
author Blasco-Brusola, A.
author_facet Blasco-Brusola, A.
Tamarit, Lorena
Navarrete-Miguel, M.
Roca-Sanjuán, Daniel
Miranda, M. A.
Vayá, Ignacio
author_role author
author2 Tamarit, Lorena
Navarrete-Miguel, M.
Roca-Sanjuán, Daniel
Miranda, M. A.
Vayá, Ignacio
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The photoinduced cycloreversion of oxetane derivatives is of considerable biological interest since these compounds are involved in the photochemical formation and repair of the highly mutagenic pyrimidine (6-4) pyrimidone DNA photoproducts ((6-4)PPs). Previous reports have dealt with the photoreactivity of heterodimeric oxetanes composed mainly of benzophenone (BP) and thymine (Thy) or uracil (Ura) derivatives. However, these models are far from the non-isolable Thy〈º〉Thy dimers, which are the real precursors of (6-4)PPs. Thus, we have synthesized two chemically stable homodimeric oxetanes through the Paternò-Büchi reaction between two identical enone units, i.e. 1,4-benzoquinone (BQ) and 1,4-naphthoquinone (NQ), that led to formation of BQ-Ox and NQ-Ox, respectively. Their photoreactivity has been studied by means of steady-state photolysis and transient absorption spectroscopy from the femtosecond to the microsecond time scale. Thus, photolysis of BQ-Ox and NQ-Ox led to formation of the monomeric BQ or NQ, respectively, through ring opening in a “non-adiabatic” process. Accordingly, the transient absorption spectra of the triplet excited quinones (BQ* and NQ*) were not observed as a result of direct photolysis of the quinone-derived oxetanes. In the case of NQ-Ox, a minor signal corresponding to NQ* was detected; its formation was ascribed to minor photodegradation of the oxetane during acquisitions of the spectra during the laser experiments. These results are supported by computational analyses based on density functional theory and multiconfigurational quantum chemistry (CASSCF/CASPT2); here, an accessible conical intersection between the ground and excited singlet states has been characterized as the main structure leading to deactivation of excited BQ-Ox or NQ-Ox. This behavior contrasts with those previously observed for heterodimeric thymine-derived oxetanes, where a certain degree of ring opening into the excited triplet state is observed.
publishDate 2024
dc.date.none.fl_str_mv 2024
2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/389110
url http://hdl.handle.net/10261/389110
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-115010RB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2021-127199NB-I00
http://dx.doi.org/10.1039/d4cp00830h
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
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