Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols

Autores
Mena, Leandro Daniel; Vera, Domingo Mariano Adolfo; Baumgartner, Maria Teresa del V.; Jimenez, Liliana Beatriz
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
ESIPT (Excited State Intramolecular Proton Transfer) to C atom in 2-phenylphenol is known to be an intrinsically inefficient process. However, to the best of our knowledge, a structure-ESIPT efficiency relationship has not been elucidated yet. Here, we show that there exists a competitive interplay between photoacidity and ESIPT efficiency for the 2-phenylphenol system. The attachment of electron withdrawing groups to the phenol moiety promotes adiabatic deprotonation in the excited state and diminishes the charge transfer character of the excitations, and both these factors contribute in decreasing the ESIPT reaction yield. On the other hand, unfavorable conformational distribution in the ground state also appears as another important aspect responsible for the low ESIPT extent of 2-phenylphenol. A new derivative bearing electron donating, bulky substituents at ortho and para positions of the phenol ring shows an outstanding ESIPT performance, which demonstrates that the efficiency of the process can be significantly enhanced by modifying the substitution pattern. We anticipate that our results will help to guide the molecular designing of new compounds with high ESIPT efficiency.
Fil: Mena, Leandro Daniel. 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
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
Fil: Jimenez, Liliana Beatriz. 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
Photoacidity;
ESIPT;
2-phenylphenol;
Adiabatic deprotonation; pKa*
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/125458
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/125458
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenolsMena, Leandro DanielVera, Domingo Mariano AdolfoBaumgartner, Maria Teresa del V.Jimenez, Liliana BeatrizPhotoacidity;ESIPT;2-phenylphenol;Adiabatic deprotonation; pKa*https://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1ESIPT (Excited State Intramolecular Proton Transfer) to C atom in 2-phenylphenol is known to be an intrinsically inefficient process. However, to the best of our knowledge, a structure-ESIPT efficiency relationship has not been elucidated yet. Here, we show that there exists a competitive interplay between photoacidity and ESIPT efficiency for the 2-phenylphenol system. The attachment of electron withdrawing groups to the phenol moiety promotes adiabatic deprotonation in the excited state and diminishes the charge transfer character of the excitations, and both these factors contribute in decreasing the ESIPT reaction yield. On the other hand, unfavorable conformational distribution in the ground state also appears as another important aspect responsible for the low ESIPT extent of 2-phenylphenol. A new derivative bearing electron donating, bulky substituents at ortho and para positions of the phenol ring shows an outstanding ESIPT performance, which demonstrates that the efficiency of the process can be significantly enhanced by modifying the substitution pattern. We anticipate that our results will help to guide the molecular designing of new compounds with high ESIPT efficiency.Fil: Mena, Leandro Daniel. 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; 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; ArgentinaFil: Jimenez, Liliana Beatriz. 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 Chemistry2019-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/125458Mena, Leandro Daniel; Vera, Domingo Mariano Adolfo; Baumgartner, Maria Teresa del V.; Jimenez, Liliana Beatriz; Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 23; 5-2019; 12231-122401463-90761463-9084CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2019/CP/C9CP02028Dinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C9CP02028Dinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:18:23Zoai:ri.conicet.gov.ar:11336/125458instacron: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:34982025-10-22 11:18:24.255CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols
title Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols
spellingShingle Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols
Mena, Leandro Daniel
Photoacidity;
ESIPT;
2-phenylphenol;
Adiabatic deprotonation; pKa*
title_short Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols
title_full Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols
title_fullStr Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols
title_full_unstemmed Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols
title_sort Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols
dc.creator.none.fl_str_mv Mena, Leandro Daniel
Vera, Domingo Mariano Adolfo
Baumgartner, Maria Teresa del V.
Jimenez, Liliana Beatriz
author Mena, Leandro Daniel
author_facet Mena, Leandro Daniel
Vera, Domingo Mariano Adolfo
Baumgartner, Maria Teresa del V.
Jimenez, Liliana Beatriz
author_role author
author2 Vera, Domingo Mariano Adolfo
Baumgartner, Maria Teresa del V.
Jimenez, Liliana Beatriz
author2_role author
author
author
dc.subject.none.fl_str_mv Photoacidity;
ESIPT;
2-phenylphenol;
Adiabatic deprotonation; pKa*
topic Photoacidity;
ESIPT;
2-phenylphenol;
Adiabatic deprotonation; pKa*
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv ESIPT (Excited State Intramolecular Proton Transfer) to C atom in 2-phenylphenol is known to be an intrinsically inefficient process. However, to the best of our knowledge, a structure-ESIPT efficiency relationship has not been elucidated yet. Here, we show that there exists a competitive interplay between photoacidity and ESIPT efficiency for the 2-phenylphenol system. The attachment of electron withdrawing groups to the phenol moiety promotes adiabatic deprotonation in the excited state and diminishes the charge transfer character of the excitations, and both these factors contribute in decreasing the ESIPT reaction yield. On the other hand, unfavorable conformational distribution in the ground state also appears as another important aspect responsible for the low ESIPT extent of 2-phenylphenol. A new derivative bearing electron donating, bulky substituents at ortho and para positions of the phenol ring shows an outstanding ESIPT performance, which demonstrates that the efficiency of the process can be significantly enhanced by modifying the substitution pattern. We anticipate that our results will help to guide the molecular designing of new compounds with high ESIPT efficiency.
Fil: Mena, Leandro Daniel. 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
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
Fil: Jimenez, Liliana Beatriz. 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 ESIPT (Excited State Intramolecular Proton Transfer) to C atom in 2-phenylphenol is known to be an intrinsically inefficient process. However, to the best of our knowledge, a structure-ESIPT efficiency relationship has not been elucidated yet. Here, we show that there exists a competitive interplay between photoacidity and ESIPT efficiency for the 2-phenylphenol system. The attachment of electron withdrawing groups to the phenol moiety promotes adiabatic deprotonation in the excited state and diminishes the charge transfer character of the excitations, and both these factors contribute in decreasing the ESIPT reaction yield. On the other hand, unfavorable conformational distribution in the ground state also appears as another important aspect responsible for the low ESIPT extent of 2-phenylphenol. A new derivative bearing electron donating, bulky substituents at ortho and para positions of the phenol ring shows an outstanding ESIPT performance, which demonstrates that the efficiency of the process can be significantly enhanced by modifying the substitution pattern. We anticipate that our results will help to guide the molecular designing of new compounds with high ESIPT efficiency.
publishDate 2019
dc.date.none.fl_str_mv 2019-05
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/11336/125458
Mena, Leandro Daniel; Vera, Domingo Mariano Adolfo; Baumgartner, Maria Teresa del V.; Jimenez, Liliana Beatriz; Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 23; 5-2019; 12231-12240
1463-9076
1463-9084
CONICET Digital
CONICET
url http://hdl.handle.net/11336/125458
identifier_str_mv Mena, Leandro Daniel; Vera, Domingo Mariano Adolfo; Baumgartner, Maria Teresa del V.; Jimenez, Liliana Beatriz; Adiabatic deprotonation as an important competing pathway to ESIPT in photoacidic 2-phenylphenols; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 21; 23; 5-2019; 12231-12240
1463-9076
1463-9084
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/Content/ArticleLanding/2019/CP/C9CP02028D
info:eu-repo/semantics/altIdentifier/doi/10.1039/C9CP02028D
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
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 12.982451

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