Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer

Autores
Mena, Leandro Daniel; Vera, Domingo Mariano Adolfo; Baumgartner, Maria Teresa del V.
Año de publicación
2020
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Hydroxyphenyl-azoles are among the most popular ESIPT (Excited State Intramolecular Proton Transfer) scaffolds and as such, they have been thoroughly studied. Nevertheless, some aspects regarding the interplay between the emissive properties of these fluorophores and the size of their π-conjugated framework remain controversial. Previous studies have demonstrated that benzannulation of 2′-hydroxyphenyl-oxazole at the phenol group of the molecule can lead to either red- or blue-shifted fluorescence emission, depending on the site where it occurs. In this report, benzannulation at the heterocyclic unit (the oxazole site) is analysed in order to get the whole picture. The extension of π-conjugation does not significantly affect the ESIPT emission wavelength, but it leads instead to higher energy barriers for proton transfer in the first excited singlet state, as a consequence of dramatic changes in the charge transfer character of excitation caused by successive benzannulation. Theoretical calculations revealed an interesting connection between intramolecular charge transfer and excited-state aromaticity in the S1 state. The theoretical approach presented herein allows the behaviour of hydroxyphenyl-oxazoles in the excited state to be rationalized and, more generally, a deeper understanding of the factors governing the ESIPT process to be obtained, a crucial point in the design of new and efficient fluorophores.
Fil: Mena, Leandro Daniel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Vera, Domingo Mariano Adolfo. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina
Fil: Baumgartner, Maria Teresa del V.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
ESIPT
PROTON TRANSFER
CHARGE TRANSFER
AROMATICITY
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/128564
Acceder
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network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transferMena, Leandro DanielVera, Domingo Mariano AdolfoBaumgartner, Maria Teresa del V.ESIPTPROTON TRANSFERCHARGE TRANSFERAROMATICITYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Hydroxyphenyl-azoles are among the most popular ESIPT (Excited State Intramolecular Proton Transfer) scaffolds and as such, they have been thoroughly studied. Nevertheless, some aspects regarding the interplay between the emissive properties of these fluorophores and the size of their π-conjugated framework remain controversial. Previous studies have demonstrated that benzannulation of 2′-hydroxyphenyl-oxazole at the phenol group of the molecule can lead to either red- or blue-shifted fluorescence emission, depending on the site where it occurs. In this report, benzannulation at the heterocyclic unit (the oxazole site) is analysed in order to get the whole picture. The extension of π-conjugation does not significantly affect the ESIPT emission wavelength, but it leads instead to higher energy barriers for proton transfer in the first excited singlet state, as a consequence of dramatic changes in the charge transfer character of excitation caused by successive benzannulation. Theoretical calculations revealed an interesting connection between intramolecular charge transfer and excited-state aromaticity in the S1 state. The theoretical approach presented herein allows the behaviour of hydroxyphenyl-oxazoles in the excited state to be rationalized and, more generally, a deeper understanding of the factors governing the ESIPT process to be obtained, a crucial point in the design of new and efficient fluorophores.Fil: Mena, Leandro Daniel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Vera, Domingo Mariano Adolfo. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; ArgentinaFil: Baumgartner, Maria Teresa del V.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaRoyal Society of Chemistry2020-10info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/128564Mena, Leandro Daniel; Vera, Domingo Mariano Adolfo; Baumgartner, Maria Teresa del V.; Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer; Royal Society of Chemistry; RSC Advances; 10; 64; 10-2020; 39049-390592046-2069CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2020/RA/D0RA05802Einfo:eu-repo/semantics/altIdentifier/doi/10.1039/D0RA05802Einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:17:02Zoai:ri.conicet.gov.ar:11336/128564instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-10 13:17:02.462CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer
title Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer
spellingShingle Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer
Mena, Leandro Daniel
ESIPT
PROTON TRANSFER
CHARGE TRANSFER
AROMATICITY
title_short Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer
title_full Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer
title_fullStr Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer
title_full_unstemmed Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer
title_sort Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer
dc.creator.none.fl_str_mv Mena, Leandro Daniel
Vera, Domingo Mariano Adolfo
Baumgartner, Maria Teresa del V.
author Mena, Leandro Daniel
author_facet Mena, Leandro Daniel
Vera, Domingo Mariano Adolfo
Baumgartner, Maria Teresa del V.
author_role author
author2 Vera, Domingo Mariano Adolfo
Baumgartner, Maria Teresa del V.
author2_role author
author
dc.subject.none.fl_str_mv ESIPT
PROTON TRANSFER
CHARGE TRANSFER
AROMATICITY
topic ESIPT
PROTON TRANSFER
CHARGE TRANSFER
AROMATICITY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Hydroxyphenyl-azoles are among the most popular ESIPT (Excited State Intramolecular Proton Transfer) scaffolds and as such, they have been thoroughly studied. Nevertheless, some aspects regarding the interplay between the emissive properties of these fluorophores and the size of their π-conjugated framework remain controversial. Previous studies have demonstrated that benzannulation of 2′-hydroxyphenyl-oxazole at the phenol group of the molecule can lead to either red- or blue-shifted fluorescence emission, depending on the site where it occurs. In this report, benzannulation at the heterocyclic unit (the oxazole site) is analysed in order to get the whole picture. The extension of π-conjugation does not significantly affect the ESIPT emission wavelength, but it leads instead to higher energy barriers for proton transfer in the first excited singlet state, as a consequence of dramatic changes in the charge transfer character of excitation caused by successive benzannulation. Theoretical calculations revealed an interesting connection between intramolecular charge transfer and excited-state aromaticity in the S1 state. The theoretical approach presented herein allows the behaviour of hydroxyphenyl-oxazoles in the excited state to be rationalized and, more generally, a deeper understanding of the factors governing the ESIPT process to be obtained, a crucial point in the design of new and efficient fluorophores.
Fil: Mena, Leandro Daniel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Vera, Domingo Mariano Adolfo. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Mar del Plata. Instituto de Investigaciones En Biodiversidad y Biotecnologia. Grupo de Investigacion En Quimica Analitica y Modelado Molecular.; Argentina
Fil: Baumgartner, Maria Teresa del V.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description Hydroxyphenyl-azoles are among the most popular ESIPT (Excited State Intramolecular Proton Transfer) scaffolds and as such, they have been thoroughly studied. Nevertheless, some aspects regarding the interplay between the emissive properties of these fluorophores and the size of their π-conjugated framework remain controversial. Previous studies have demonstrated that benzannulation of 2′-hydroxyphenyl-oxazole at the phenol group of the molecule can lead to either red- or blue-shifted fluorescence emission, depending on the site where it occurs. In this report, benzannulation at the heterocyclic unit (the oxazole site) is analysed in order to get the whole picture. The extension of π-conjugation does not significantly affect the ESIPT emission wavelength, but it leads instead to higher energy barriers for proton transfer in the first excited singlet state, as a consequence of dramatic changes in the charge transfer character of excitation caused by successive benzannulation. Theoretical calculations revealed an interesting connection between intramolecular charge transfer and excited-state aromaticity in the S1 state. The theoretical approach presented herein allows the behaviour of hydroxyphenyl-oxazoles in the excited state to be rationalized and, more generally, a deeper understanding of the factors governing the ESIPT process to be obtained, a crucial point in the design of new and efficient fluorophores.
publishDate 2020
dc.date.none.fl_str_mv 2020-10
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/128564
Mena, Leandro Daniel; Vera, Domingo Mariano Adolfo; Baumgartner, Maria Teresa del V.; Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer; Royal Society of Chemistry; RSC Advances; 10; 64; 10-2020; 39049-39059
2046-2069
CONICET Digital
CONICET
url http://hdl.handle.net/11336/128564
identifier_str_mv Mena, Leandro Daniel; Vera, Domingo Mariano Adolfo; Baumgartner, Maria Teresa del V.; Impact of benzannulation on ESIPT in 2-(2′-hydroxyphenyl)-oxazoles: A unified perspective in terms of excited-state aromaticity and intramolecular charge transfer; Royal Society of Chemistry; RSC Advances; 10; 64; 10-2020; 39049-39059
2046-2069
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2020/RA/D0RA05802E
info:eu-repo/semantics/altIdentifier/doi/10.1039/D0RA05802E
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.993085

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