Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques

Autores
Ragone, Fabricio; Martínez Saavedra, Héctor Hernando; David Gara, Pedro Maximiliano; Ruiz, Gustavo Teodosio; Wolcan, Ezequiel
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Quantum yields and efficiencies of 1O2 (1Δg) production along with photophysical properties for a number of Re(I) complexes in acetonitrile solutions are reported. Two different classes of Re(I) complexes, LS-CO2-Re(CO)3(bpy) (LS = 2-pyrazine, 2-naphthalene, 9-anthracene, 1-pyrene, 2-anthraquinone) and XRe(CO)3L (X =CF3SO3, py; L = bpy, phen), were probed as photosensitizers for 1O2 (1Δg) production in air-saturated acetonitrile solutions. Depending on the nature of the Re(I) complex, the excited state responsible for the generation of 1O2 (1Δg) is either a metal-to-ligand charge transfer (3MLCT) or a ligand centered (3LC) state. With LS-CO2-Re(CO)3(bpy)complexes, 1O2 (1Δg) is produced by oxygen quenching of 3LC states of anthracene and pyrene with high quantum yields (ΦΔ between 0.8 and 1.0), while the complexes bearing the ligands LS = 2-anthraquinone, 2-pyrazine, and 2-naphthalene did not yield 1O2. XRe(CO)3L complexes generate 1O2 (1Δg) mainly by oxygen quenching of their 3MLCT luminescence with an efficiency of 1O2 (1Δg) formation close to unity. Bimolecular rate constants for the quenching of the XRe(CO)3L complexes? emission by molecular oxygen range between 1 × 109 and 2 × 109 M−1 s−1, and they are all ≤ 1/9kd,in good agreement with the predominance of the singlet channel in the mechanism of 1O2 (1Δg) generation using these Re(I)complexes as photosensitizers. All the experimental singlet oxygen efficiencies are consistent with calorimetric and luminescence data for the studied complexes. With LS-CO2-Re(CO)3(bpy) complexes, calorimetric experiments were utilized in the calculation of the quantum yields of triplet formation; namely ϕT = 0.76 and 0.83 for the triplet states of anthracene and pyrene, respectively.
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: 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: 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: 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: 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
Lioas
Singlet Oxygen
Rhenium
Triplet
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:11336/5140
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence TechniquesRagone, FabricioMartínez Saavedra, Héctor HernandoDavid Gara, Pedro MaximilianoRuiz, Gustavo TeodosioWolcan, EzequielLioasSinglet OxygenRheniumTriplethttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Quantum yields and efficiencies of 1O2 (1Δg) production along with photophysical properties for a number of Re(I) complexes in acetonitrile solutions are reported. Two different classes of Re(I) complexes, LS-CO2-Re(CO)3(bpy) (LS = 2-pyrazine, 2-naphthalene, 9-anthracene, 1-pyrene, 2-anthraquinone) and XRe(CO)3L (X =CF3SO3, py; L = bpy, phen), were probed as photosensitizers for 1O2 (1Δg) production in air-saturated acetonitrile solutions. Depending on the nature of the Re(I) complex, the excited state responsible for the generation of 1O2 (1Δg) is either a metal-to-ligand charge transfer (3MLCT) or a ligand centered (3LC) state. With LS-CO2-Re(CO)3(bpy)complexes, 1O2 (1Δg) is produced by oxygen quenching of 3LC states of anthracene and pyrene with high quantum yields (ΦΔ between 0.8 and 1.0), while the complexes bearing the ligands LS = 2-anthraquinone, 2-pyrazine, and 2-naphthalene did not yield 1O2. XRe(CO)3L complexes generate 1O2 (1Δg) mainly by oxygen quenching of their 3MLCT luminescence with an efficiency of 1O2 (1Δg) formation close to unity. Bimolecular rate constants for the quenching of the XRe(CO)3L complexes? emission by molecular oxygen range between 1 × 109 and 2 × 109 M−1 s−1, and they are all ≤ 1/9kd,in good agreement with the predominance of the singlet channel in the mechanism of 1O2 (1Δg) generation using these Re(I)complexes as photosensitizers. All the experimental singlet oxygen efficiencies are consistent with calorimetric and luminescence data for the studied complexes. With LS-CO2-Re(CO)3(bpy) complexes, calorimetric experiments were utilized in the calculation of the quantum yields of triplet formation; namely ϕT = 0.76 and 0.83 for the triplet states of anthracene and pyrene, respectively.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; ArgentinaFil: 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: 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: 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: 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 Society2013-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/5140Ragone, Fabricio; Martínez Saavedra, Héctor Hernando; David Gara, Pedro Maximiliano; Ruiz, Gustavo Teodosio; Wolcan, Ezequiel; Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques; American Chemical Society; Journal Of Physical Chemistry A; 117; 21; 5-2013; 4428-44351089-5639enginfo:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp402550ginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp402550ginfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:53:50Zoai:ri.conicet.gov.ar:11336/5140instacron: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:34982025-09-03 09:53:50.961CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques
title Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques
spellingShingle Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques
Ragone, Fabricio
Lioas
Singlet Oxygen
Rhenium
Triplet
title_short Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques
title_full Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques
title_fullStr Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques
title_full_unstemmed Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques
title_sort Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques
dc.creator.none.fl_str_mv Ragone, Fabricio
Martínez Saavedra, Héctor Hernando
David Gara, Pedro Maximiliano
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
author Ragone, Fabricio
author_facet Ragone, Fabricio
Martínez Saavedra, Héctor Hernando
David Gara, Pedro Maximiliano
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
author_role author
author2 Martínez Saavedra, Héctor Hernando
David Gara, Pedro Maximiliano
Ruiz, Gustavo Teodosio
Wolcan, Ezequiel
author2_role author
author
author
author
dc.subject.none.fl_str_mv Lioas
Singlet Oxygen
Rhenium
Triplet
topic Lioas
Singlet Oxygen
Rhenium
Triplet
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Quantum yields and efficiencies of 1O2 (1Δg) production along with photophysical properties for a number of Re(I) complexes in acetonitrile solutions are reported. Two different classes of Re(I) complexes, LS-CO2-Re(CO)3(bpy) (LS = 2-pyrazine, 2-naphthalene, 9-anthracene, 1-pyrene, 2-anthraquinone) and XRe(CO)3L (X =CF3SO3, py; L = bpy, phen), were probed as photosensitizers for 1O2 (1Δg) production in air-saturated acetonitrile solutions. Depending on the nature of the Re(I) complex, the excited state responsible for the generation of 1O2 (1Δg) is either a metal-to-ligand charge transfer (3MLCT) or a ligand centered (3LC) state. With LS-CO2-Re(CO)3(bpy)complexes, 1O2 (1Δg) is produced by oxygen quenching of 3LC states of anthracene and pyrene with high quantum yields (ΦΔ between 0.8 and 1.0), while the complexes bearing the ligands LS = 2-anthraquinone, 2-pyrazine, and 2-naphthalene did not yield 1O2. XRe(CO)3L complexes generate 1O2 (1Δg) mainly by oxygen quenching of their 3MLCT luminescence with an efficiency of 1O2 (1Δg) formation close to unity. Bimolecular rate constants for the quenching of the XRe(CO)3L complexes? emission by molecular oxygen range between 1 × 109 and 2 × 109 M−1 s−1, and they are all ≤ 1/9kd,in good agreement with the predominance of the singlet channel in the mechanism of 1O2 (1Δg) generation using these Re(I)complexes as photosensitizers. All the experimental singlet oxygen efficiencies are consistent with calorimetric and luminescence data for the studied complexes. With LS-CO2-Re(CO)3(bpy) complexes, calorimetric experiments were utilized in the calculation of the quantum yields of triplet formation; namely ϕT = 0.76 and 0.83 for the triplet states of anthracene and pyrene, respectively.
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: 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: 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: 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: 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 Quantum yields and efficiencies of 1O2 (1Δg) production along with photophysical properties for a number of Re(I) complexes in acetonitrile solutions are reported. Two different classes of Re(I) complexes, LS-CO2-Re(CO)3(bpy) (LS = 2-pyrazine, 2-naphthalene, 9-anthracene, 1-pyrene, 2-anthraquinone) and XRe(CO)3L (X =CF3SO3, py; L = bpy, phen), were probed as photosensitizers for 1O2 (1Δg) production in air-saturated acetonitrile solutions. Depending on the nature of the Re(I) complex, the excited state responsible for the generation of 1O2 (1Δg) is either a metal-to-ligand charge transfer (3MLCT) or a ligand centered (3LC) state. With LS-CO2-Re(CO)3(bpy)complexes, 1O2 (1Δg) is produced by oxygen quenching of 3LC states of anthracene and pyrene with high quantum yields (ΦΔ between 0.8 and 1.0), while the complexes bearing the ligands LS = 2-anthraquinone, 2-pyrazine, and 2-naphthalene did not yield 1O2. XRe(CO)3L complexes generate 1O2 (1Δg) mainly by oxygen quenching of their 3MLCT luminescence with an efficiency of 1O2 (1Δg) formation close to unity. Bimolecular rate constants for the quenching of the XRe(CO)3L complexes? emission by molecular oxygen range between 1 × 109 and 2 × 109 M−1 s−1, and they are all ≤ 1/9kd,in good agreement with the predominance of the singlet channel in the mechanism of 1O2 (1Δg) generation using these Re(I)complexes as photosensitizers. All the experimental singlet oxygen efficiencies are consistent with calorimetric and luminescence data for the studied complexes. With LS-CO2-Re(CO)3(bpy) complexes, calorimetric experiments were utilized in the calculation of the quantum yields of triplet formation; namely ϕT = 0.76 and 0.83 for the triplet states of anthracene and pyrene, respectively.
publishDate 2013
dc.date.none.fl_str_mv 2013-05
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/11336/5140
Ragone, Fabricio; Martínez Saavedra, Héctor Hernando; David Gara, Pedro Maximiliano; Ruiz, Gustavo Teodosio; Wolcan, Ezequiel; Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques; American Chemical Society; Journal Of Physical Chemistry A; 117; 21; 5-2013; 4428-4435
1089-5639
url http://hdl.handle.net/11336/5140
identifier_str_mv Ragone, Fabricio; Martínez Saavedra, Héctor Hernando; David Gara, Pedro Maximiliano; Ruiz, Gustavo Teodosio; Wolcan, Ezequiel; Photosensitized Generation of Singlet Oxygen from Re(I) Complexes: A Photophysical Study Using LIOAS and Luminescence Techniques; American Chemical Society; Journal Of Physical Chemistry A; 117; 21; 5-2013; 4428-4435
1089-5639
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp402550g
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp402550g
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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eu_rights_str_mv openAccess
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application/pdf
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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)
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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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