Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study

Autores
Martínez Saavedra, Héctor Hernando; Ragone, Fabricio; Ruiz, Gustavo Teodosio; David Gara, Pedro Maximiliano; Wolcan, Ezequiel
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Steady state and time-resolved luminescence experiments and calorimetric studies, as well as time-dependent density functional theory calculations performed on [ClRe(CO)3(Bathocuproinedisulfonate)]2−, show that the photophysical properties of the Re(I) anionic complex are determined by the balance between intraligand (1IL) and metal−ligand-to-ligand charge transfer (3MLLCT) excited states. In organic solvents, 3MLLCT states prevail and the usual expected behavior is observed: bathochromic shift of the emission maximum, a reduced luminescence quantum yield and the shortening of the excited-state lifetime upon increasing the polarity of the solvent. In addition, singlet oxygen (1O2) is generated with high quantum yields (ΦΔ ≈ 0.5 in CH3CN) due to the quenching of the 3MLLCT luminescence by 3O2. The total quenching rate constant of triplet state by oxygen, kq,reach values between 2.2 and 2.4 × 109 M−1 s−1 for the organic solvents studied. In CH3CN, the fraction of triplet states quenched by O2 which yield 1O2, f O2T , is nearly unity. In aqueous solution, where no singlet oxygen is generated, the luminescence of the Re(I) complex is of 1IL character with a emission quantum yield (Φem) strongly pH dependent: Φem,(pH=2)/Φem,(pH=10) ≈ 5.6. The variation of the pH of the solution tunes the photophysical properties of the Re(I) complex by changing the relative amount of the different species existing in aqueous solutions:[ClRe(CO)3(BCS)]2−, [(OH)Re(CO)3(BCS)]2− and [(H2O)Re(CO)3(BCS)]−. TD-DFT calculations show that the percentage of charge transfer character of the electronic transitions is substantially higher in the organic solvents than in aqueous solutions, in agreement with the increase of 1IL character of HOMO in [(H2O)Re(CO)3(BCS)]− relative to [ClRe(CO)3(BCS)]2−.
Fil: Martínez Saavedra, Héctor Hernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Ragone, Fabricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: David Gara, Pedro Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Centro de Investigaciones Opticas (i); Argentina. Universidad Nacional de La Plata; Argentina
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Materia
Baocuproina
Complejos
Organometalicos
Fotoquimica
Nivel de accesibilidad
acceso abierto
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https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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CONICET Digital (CONICET)
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Consejo Nacional de Investigaciones Científicas y Técnicas
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oai:ri.conicet.gov.ar:11336/5012
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational studyMartínez Saavedra, Héctor HernandoRagone, FabricioRuiz, Gustavo TeodosioDavid Gara, Pedro MaximilianoWolcan, EzequielBaocuproinaComplejosOrganometalicosFotoquimicahttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Steady state and time-resolved luminescence experiments and calorimetric studies, as well as time-dependent density functional theory calculations performed on [ClRe(CO)3(Bathocuproinedisulfonate)]2−, show that the photophysical properties of the Re(I) anionic complex are determined by the balance between intraligand (1IL) and metal−ligand-to-ligand charge transfer (3MLLCT) excited states. In organic solvents, 3MLLCT states prevail and the usual expected behavior is observed: bathochromic shift of the emission maximum, a reduced luminescence quantum yield and the shortening of the excited-state lifetime upon increasing the polarity of the solvent. In addition, singlet oxygen (1O2) is generated with high quantum yields (ΦΔ ≈ 0.5 in CH3CN) due to the quenching of the 3MLLCT luminescence by 3O2. The total quenching rate constant of triplet state by oxygen, kq,reach values between 2.2 and 2.4 × 109 M−1 s−1 for the organic solvents studied. In CH3CN, the fraction of triplet states quenched by O2 which yield 1O2, f O2T , is nearly unity. In aqueous solution, where no singlet oxygen is generated, the luminescence of the Re(I) complex is of 1IL character with a emission quantum yield (Φem) strongly pH dependent: Φem,(pH=2)/Φem,(pH=10) ≈ 5.6. The variation of the pH of the solution tunes the photophysical properties of the Re(I) complex by changing the relative amount of the different species existing in aqueous solutions:[ClRe(CO)3(BCS)]2−, [(OH)Re(CO)3(BCS)]2− and [(H2O)Re(CO)3(BCS)]−. TD-DFT calculations show that the percentage of charge transfer character of the electronic transitions is substantially higher in the organic solvents than in aqueous solutions, in agreement with the increase of 1IL character of HOMO in [(H2O)Re(CO)3(BCS)]− relative to [ClRe(CO)3(BCS)]2−.Fil: Martínez Saavedra, Héctor Hernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Ragone, Fabricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: David Gara, Pedro Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Centro de Investigaciones Opticas (i); Argentina. Universidad Nacional de La Plata; ArgentinaFil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; ArgentinaAmerican Chemical Society2014-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/5012Martínez Saavedra, Héctor Hernando; Ragone, Fabricio; Ruiz, Gustavo Teodosio; David Gara, Pedro Maximiliano; Wolcan, Ezequiel; Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study; American Chemical Society; Journal Of Physical Chemistry A; 118; 9-2014; 9661-96741089-5639enginfo:eu-repo/semantics/altIdentifier/pmid/25233269info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/pdf/10.1021/jp506890rinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp506890rinfo:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:14:57Zoai:ri.conicet.gov.ar:11336/5012instacron: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 12:14:57.741CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study
title Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study
spellingShingle Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study
Martínez Saavedra, Héctor Hernando
Baocuproina
Complejos
Organometalicos
Fotoquimica
title_short Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study
title_full Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study
title_fullStr Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study
title_full_unstemmed Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study
title_sort Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study
dc.creator.none.fl_str_mv Martínez Saavedra, Héctor Hernando
Ragone, Fabricio
Ruiz, Gustavo Teodosio
David Gara, Pedro Maximiliano
Wolcan, Ezequiel
author Martínez Saavedra, Héctor Hernando
author_facet Martínez Saavedra, Héctor Hernando
Ragone, Fabricio
Ruiz, Gustavo Teodosio
David Gara, Pedro Maximiliano
Wolcan, Ezequiel
author_role author
author2 Ragone, Fabricio
Ruiz, Gustavo Teodosio
David Gara, Pedro Maximiliano
Wolcan, Ezequiel
author2_role author
author
author
author
dc.subject.none.fl_str_mv Baocuproina
Complejos
Organometalicos
Fotoquimica
topic Baocuproina
Complejos
Organometalicos
Fotoquimica
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Steady state and time-resolved luminescence experiments and calorimetric studies, as well as time-dependent density functional theory calculations performed on [ClRe(CO)3(Bathocuproinedisulfonate)]2−, show that the photophysical properties of the Re(I) anionic complex are determined by the balance between intraligand (1IL) and metal−ligand-to-ligand charge transfer (3MLLCT) excited states. In organic solvents, 3MLLCT states prevail and the usual expected behavior is observed: bathochromic shift of the emission maximum, a reduced luminescence quantum yield and the shortening of the excited-state lifetime upon increasing the polarity of the solvent. In addition, singlet oxygen (1O2) is generated with high quantum yields (ΦΔ ≈ 0.5 in CH3CN) due to the quenching of the 3MLLCT luminescence by 3O2. The total quenching rate constant of triplet state by oxygen, kq,reach values between 2.2 and 2.4 × 109 M−1 s−1 for the organic solvents studied. In CH3CN, the fraction of triplet states quenched by O2 which yield 1O2, f O2T , is nearly unity. In aqueous solution, where no singlet oxygen is generated, the luminescence of the Re(I) complex is of 1IL character with a emission quantum yield (Φem) strongly pH dependent: Φem,(pH=2)/Φem,(pH=10) ≈ 5.6. The variation of the pH of the solution tunes the photophysical properties of the Re(I) complex by changing the relative amount of the different species existing in aqueous solutions:[ClRe(CO)3(BCS)]2−, [(OH)Re(CO)3(BCS)]2− and [(H2O)Re(CO)3(BCS)]−. TD-DFT calculations show that the percentage of charge transfer character of the electronic transitions is substantially higher in the organic solvents than in aqueous solutions, in agreement with the increase of 1IL character of HOMO in [(H2O)Re(CO)3(BCS)]− relative to [ClRe(CO)3(BCS)]2−.
Fil: Martínez Saavedra, Héctor Hernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Ragone, Fabricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
Fil: David Gara, Pedro Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Centro de Investigaciones Opticas (i); Argentina. Universidad Nacional de La Plata; Argentina
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico la Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Universidad Nacional de La Plata; Argentina
description Steady state and time-resolved luminescence experiments and calorimetric studies, as well as time-dependent density functional theory calculations performed on [ClRe(CO)3(Bathocuproinedisulfonate)]2−, show that the photophysical properties of the Re(I) anionic complex are determined by the balance between intraligand (1IL) and metal−ligand-to-ligand charge transfer (3MLLCT) excited states. In organic solvents, 3MLLCT states prevail and the usual expected behavior is observed: bathochromic shift of the emission maximum, a reduced luminescence quantum yield and the shortening of the excited-state lifetime upon increasing the polarity of the solvent. In addition, singlet oxygen (1O2) is generated with high quantum yields (ΦΔ ≈ 0.5 in CH3CN) due to the quenching of the 3MLLCT luminescence by 3O2. The total quenching rate constant of triplet state by oxygen, kq,reach values between 2.2 and 2.4 × 109 M−1 s−1 for the organic solvents studied. In CH3CN, the fraction of triplet states quenched by O2 which yield 1O2, f O2T , is nearly unity. In aqueous solution, where no singlet oxygen is generated, the luminescence of the Re(I) complex is of 1IL character with a emission quantum yield (Φem) strongly pH dependent: Φem,(pH=2)/Φem,(pH=10) ≈ 5.6. The variation of the pH of the solution tunes the photophysical properties of the Re(I) complex by changing the relative amount of the different species existing in aqueous solutions:[ClRe(CO)3(BCS)]2−, [(OH)Re(CO)3(BCS)]2− and [(H2O)Re(CO)3(BCS)]−. TD-DFT calculations show that the percentage of charge transfer character of the electronic transitions is substantially higher in the organic solvents than in aqueous solutions, in agreement with the increase of 1IL character of HOMO in [(H2O)Re(CO)3(BCS)]− relative to [ClRe(CO)3(BCS)]2−.
publishDate 2014
dc.date.none.fl_str_mv 2014-09
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/11336/5012
Martínez Saavedra, Héctor Hernando; Ragone, Fabricio; Ruiz, Gustavo Teodosio; David Gara, Pedro Maximiliano; Wolcan, Ezequiel; Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study; American Chemical Society; Journal Of Physical Chemistry A; 118; 9-2014; 9661-9674
1089-5639
url http://hdl.handle.net/11336/5012
identifier_str_mv Martínez Saavedra, Héctor Hernando; Ragone, Fabricio; Ruiz, Gustavo Teodosio; David Gara, Pedro Maximiliano; Wolcan, Ezequiel; Solvent dependent switching of 3MLLCT and 1IL luminescent states in [ClRe(CO)3(Bathocuproinedisulfonate)]2-: Spectroscopic and computational study; American Chemical Society; Journal Of Physical Chemistry A; 118; 9-2014; 9661-9674
1089-5639
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/pmid/25233269
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/pdf/10.1021/jp506890r
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp506890r
info:eu-repo/semantics/altIdentifier/doi/
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
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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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