Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies

The development of fluorescence materials with switched on/of f emission has attracted great attention owing to the potential application of these materials in chemical sensing. In this work, the photophysical properties of a series of original 2-(2′- hydroxyphenyl)pyrimidines were thoroughly studie...

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Autores: Plaza-Pedroche, Rodrigo, Fernandez-Liencres, M Paz, Jimenez-Pulido, Sonia B., Illan-cabeza, Nuria A., Achelle, Sylvain, Navarro, Amparo, Rodriguez-Lopez, Julian
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2022
País:España
Institución:Universidad de Jaén
Repositorio:RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaén
OAI Identifier:oai:ruja.ujaen.es:10953/7132
Acceso en línea:https://doi.org/10.1021/acsami.2c05439
https://hdl.handle.net/10953/7132
Access Level:acceso abierto
Palabra clave:ESIPT
pyrimidines
fluorescence
TD-DFT
anticounterfeiting
544
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repository_id_str
spelling Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical StudiesPlaza-Pedroche, RodrigoFernandez-Liencres, M PazJimenez-Pulido, Sonia B.Illan-cabeza, Nuria A.Achelle, SylvainNavarro, AmparoRodriguez-Lopez, JulianESIPTpyrimidinesfluorescenceTD-DFTanticounterfeiting544The development of fluorescence materials with switched on/of f emission has attracted great attention owing to the potential application of these materials in chemical sensing. In this work, the photophysical properties of a series of original 2-(2′- hydroxyphenyl)pyrimidines were thoroughly studied. The compounds were prepared by following well-established and straightforward methodologies and showed very little or null photoluminescence both in solution and in the solid state. This absence of emission can be explained by a fast proton transfer from the OH group to the nitrogen atoms of the pyrimidine ring to yield an excited tautomer that deactivates through a nonradiative pathway. The key role of the OH group in the emission quenching was demonstrated by the preparation of 2′-unsubstituted derivatives, all of which exhibited violet or blue luminescence. Single crystals of some compounds suitable for an X-ray diffraction analysis could be obtained, which permitted us to investigate inter- and intramolecular interactions and molecular packing structures. The protonation of the pyrimidine ring by an addition of trifluoroacetic acid inhibited the excited-state intramolecular proton transfer (ESIPT) process, causing a reversible switch on fluorescence response detectable by the naked eye. This acidochromic behavior allows 2-(2′-hydroxyphenyl)pyrimidines to be used as solid-state acid−base vapor sensors and anticounterfeiting agents. Extensive density functional theory and its time-dependent counterpart calculations at the M06-2X/6-31+G** level of theory were performed to rationalize all the experimental results and understand the impact of protonation on the different optical transitions.Funding from the Junta de Comunidades de Castilla-La Mancha/FEDER (Project No. SBPLY/17/180501/000214) is gratefully acknowledged. The Consejería de Transformación Económica, Industria, Conocimiento y Universidades/Junta de Andalucía (FQM-337) and the Universidad de Jaén (Acción 1) are also thanked for supporting the research described in this article. The Centro de Servicios de Informática y Redes de Comunicaciones (CSIRC, Universidad de Granada) was instrumental in providing the computer time that made this work possible.American Chemical Society202620262022info:eu-repo/semantics/articleinfo:eu-repo/semantics/acceptedVersionapplication/pdfhttps://doi.org/10.1021/acsami.2c05439https://hdl.handle.net/10953/7132reponame:RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaéninstname:Universidad de JaénInglésACD Applied Materials & InterfacesAttribution-NonCommercial-NoDerivs 3.0 Spainhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccessoai:ruja.ujaen.es:10953/71322026-06-24T12:41:07Z
dc.title.none.fl_str_mv Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies
title Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies
spellingShingle Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies
Plaza-Pedroche, Rodrigo
ESIPT
pyrimidines
fluorescence
TD-DFT
anticounterfeiting
544
title_short Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies
title_full Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies
title_fullStr Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies
title_full_unstemmed Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies
title_sort Excited-State Intramolecular Proton Transfer in 2‑(2′- Hydroxyphenyl)pyrimidines: Synthesis, Optical Properties, and Theoretical Studies
dc.creator.none.fl_str_mv Plaza-Pedroche, Rodrigo
Fernandez-Liencres, M Paz
Jimenez-Pulido, Sonia B.
Illan-cabeza, Nuria A.
Achelle, Sylvain
Navarro, Amparo
Rodriguez-Lopez, Julian
author Plaza-Pedroche, Rodrigo
author_facet Plaza-Pedroche, Rodrigo
Fernandez-Liencres, M Paz
Jimenez-Pulido, Sonia B.
Illan-cabeza, Nuria A.
Achelle, Sylvain
Navarro, Amparo
Rodriguez-Lopez, Julian
author_role author
author2 Fernandez-Liencres, M Paz
Jimenez-Pulido, Sonia B.
Illan-cabeza, Nuria A.
Achelle, Sylvain
Navarro, Amparo
Rodriguez-Lopez, Julian
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv ESIPT
pyrimidines
fluorescence
TD-DFT
anticounterfeiting
544
topic ESIPT
pyrimidines
fluorescence
TD-DFT
anticounterfeiting
544
description The development of fluorescence materials with switched on/of f emission has attracted great attention owing to the potential application of these materials in chemical sensing. In this work, the photophysical properties of a series of original 2-(2′- hydroxyphenyl)pyrimidines were thoroughly studied. The compounds were prepared by following well-established and straightforward methodologies and showed very little or null photoluminescence both in solution and in the solid state. This absence of emission can be explained by a fast proton transfer from the OH group to the nitrogen atoms of the pyrimidine ring to yield an excited tautomer that deactivates through a nonradiative pathway. The key role of the OH group in the emission quenching was demonstrated by the preparation of 2′-unsubstituted derivatives, all of which exhibited violet or blue luminescence. Single crystals of some compounds suitable for an X-ray diffraction analysis could be obtained, which permitted us to investigate inter- and intramolecular interactions and molecular packing structures. The protonation of the pyrimidine ring by an addition of trifluoroacetic acid inhibited the excited-state intramolecular proton transfer (ESIPT) process, causing a reversible switch on fluorescence response detectable by the naked eye. This acidochromic behavior allows 2-(2′-hydroxyphenyl)pyrimidines to be used as solid-state acid−base vapor sensors and anticounterfeiting agents. Extensive density functional theory and its time-dependent counterpart calculations at the M06-2X/6-31+G** level of theory were performed to rationalize all the experimental results and understand the impact of protonation on the different optical transitions.
publishDate 2022
dc.date.none.fl_str_mv 2022
2026
2026
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/acceptedVersion
format article
status_str acceptedVersion
dc.identifier.none.fl_str_mv https://doi.org/10.1021/acsami.2c05439
https://hdl.handle.net/10953/7132
url https://doi.org/10.1021/acsami.2c05439
https://hdl.handle.net/10953/7132
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv ACD Applied Materials & Interfaces
dc.rights.none.fl_str_mv Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
info:eu-repo/semantics/openAccess
rights_invalid_str_mv Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaén
instname:Universidad de Jaén
instname_str Universidad de Jaén
reponame_str RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaén
collection RUJA. Repositorio Institucional de la Producción Científica de la Universidad de Jaén
repository.name.fl_str_mv
repository.mail.fl_str_mv
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