Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity

Autores
Maisuls, Iván; Wolcan, Ezequiel; David Gara, Pedro Maximiliano; Cabrerizo, Franco Martín; Ferraudi, Guillermo J.; Ruiz, Gustavo Teodosio
Año de publicación
2021
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The photochemical and photophysical properties of a Re(I) tricarbonyl complex, ClRe(CO)3(nHo)2, where nHo = 9H-pyrido[3,4-b] indole (norharmane), were investigated in solution phase by a combination of steady state emission spectroscopy, laser flash photolysis (LFP) and pulse radiolysis (PR) techniques. These results allowed us to identify and study the reactivity of the β-carboline (nHo) Rhenium(I) complex main excited states. The absorption spectrum as well as the steady-state and time-resolved luminescence of the complex exhibits a marked dependence with the solvent properties. These experimentally observed results were corroborated by quantum chemical calculations, TD-DFT. The most important electronic transitions present in the spectrum in all solvents are MLLCTRe(CO)3→nHo1, nHo2 along with a mixture of ILnHo and LLCTCl→nHo transitions. The relationship between the dipole moment and the polarity of the solvent was rationalized in terms of the electron density inside and outside the complex. While the luminescence of the complex is mainly attributed to the emitting 1ILnHo state, in LFP experiments a MLCT excited state was also detected. The species generated in either reductive or oxidative conditions in LFP experiments were compared with those obtained in PR. Also, the quenching rate constant (kq) of the excited state with MV+2 was calculated. The excited state of the complex can efficiently generate singlet oxygen in acetonitrile yielding a ΦΔ = 0.25 ± 0.02. Optoacoustic measurements showed that, after photonic excitation, almost all the absorbed energy by the complex is released to the medium as prompt heat. The investigated photophysical and photochemical properties of ClRe(CO)3(nHo)2 are of significant importance in relation to the use of this β-carboline Rhenium(I) complex in several biomedical fields, such as photodynamic therapy and photoactivated chemotherapy as well as new alternative therapies such as regional hyperthermia.
Fil: Maisuls, Iván. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: David Gara, Pedro Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones Ópticas. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones Ópticas. Universidad Nacional de La Plata. Centro de Investigaciones Ópticas; Argentina
Fil: Cabrerizo, Franco Martín. Universidad Nacional de San Martin. Instituto Tecnologico de Chascomus. - Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - la Plata. Instituto Tecnologico de Chascomus.; Argentina
Fil: Ferraudi, Guillermo J.. University of Notre Dame; Estados Unidos
Fil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
NORHARMANE – TD-DFT
PHOTOCHEMISTRY
PHOTOPHYSICS
PULSE RADIOLYSIS
RHENIUM TRICARBONYL COMPLEXES
SINGLET OXYGEN GENERATION
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/164152
Acceder
id CONICETDig_c0244fd3394ac97ca0c3e841696a707f
oai_identifier_str oai:ri.conicet.gov.ar:11336/164152
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivityMaisuls, IvánWolcan, EzequielDavid Gara, Pedro MaximilianoCabrerizo, Franco MartínFerraudi, Guillermo J.Ruiz, Gustavo TeodosioNORHARMANE – TD-DFTPHOTOCHEMISTRYPHOTOPHYSICSPULSE RADIOLYSISRHENIUM TRICARBONYL COMPLEXESSINGLET OXYGEN GENERATIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The photochemical and photophysical properties of a Re(I) tricarbonyl complex, ClRe(CO)3(nHo)2, where nHo = 9H-pyrido[3,4-b] indole (norharmane), were investigated in solution phase by a combination of steady state emission spectroscopy, laser flash photolysis (LFP) and pulse radiolysis (PR) techniques. These results allowed us to identify and study the reactivity of the β-carboline (nHo) Rhenium(I) complex main excited states. The absorption spectrum as well as the steady-state and time-resolved luminescence of the complex exhibits a marked dependence with the solvent properties. These experimentally observed results were corroborated by quantum chemical calculations, TD-DFT. The most important electronic transitions present in the spectrum in all solvents are MLLCTRe(CO)3→nHo1, nHo2 along with a mixture of ILnHo and LLCTCl→nHo transitions. The relationship between the dipole moment and the polarity of the solvent was rationalized in terms of the electron density inside and outside the complex. While the luminescence of the complex is mainly attributed to the emitting 1ILnHo state, in LFP experiments a MLCT excited state was also detected. The species generated in either reductive or oxidative conditions in LFP experiments were compared with those obtained in PR. Also, the quenching rate constant (kq) of the excited state with MV+2 was calculated. The excited state of the complex can efficiently generate singlet oxygen in acetonitrile yielding a ΦΔ = 0.25 ± 0.02. Optoacoustic measurements showed that, after photonic excitation, almost all the absorbed energy by the complex is released to the medium as prompt heat. The investigated photophysical and photochemical properties of ClRe(CO)3(nHo)2 are of significant importance in relation to the use of this β-carboline Rhenium(I) complex in several biomedical fields, such as photodynamic therapy and photoactivated chemotherapy as well as new alternative therapies such as regional hyperthermia.Fil: Maisuls, Iván. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); ArgentinaFil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: David Gara, Pedro Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones Ópticas. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones Ópticas. Universidad Nacional de La Plata. Centro de Investigaciones Ópticas; ArgentinaFil: Cabrerizo, Franco Martín. Universidad Nacional de San Martin. Instituto Tecnologico de Chascomus. - Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - la Plata. Instituto Tecnologico de Chascomus.; ArgentinaFil: Ferraudi, Guillermo J.. University of Notre Dame; Estados UnidosFil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaElsevier2021-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/164152Maisuls, Iván; Wolcan, Ezequiel; David Gara, Pedro Maximiliano; Cabrerizo, Franco Martín; Ferraudi, Guillermo J.; et al.; Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity; Elsevier; Journal of Photochemistry and Photobiology; 8; 100078; 12-2021; 1-102666-4690CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://linkinghub.elsevier.com/retrieve/pii/S2666469021000634info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jpap.2021.100078info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:55:42Zoai:ri.conicet.gov.ar:11336/164152instacron: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:34982025-09-29 09:55:43.035CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
spellingShingle Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
Maisuls, Iván
NORHARMANE – TD-DFT
PHOTOCHEMISTRY
PHOTOPHYSICS
PULSE RADIOLYSIS
RHENIUM TRICARBONYL COMPLEXES
SINGLET OXYGEN GENERATION
title_short Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_full Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_fullStr Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_full_unstemmed Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
title_sort Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity
dc.creator.none.fl_str_mv Maisuls, Iván
Wolcan, Ezequiel
David Gara, Pedro Maximiliano
Cabrerizo, Franco Martín
Ferraudi, Guillermo J.
Ruiz, Gustavo Teodosio
author Maisuls, Iván
author_facet Maisuls, Iván
Wolcan, Ezequiel
David Gara, Pedro Maximiliano
Cabrerizo, Franco Martín
Ferraudi, Guillermo J.
Ruiz, Gustavo Teodosio
author_role author
author2 Wolcan, Ezequiel
David Gara, Pedro Maximiliano
Cabrerizo, Franco Martín
Ferraudi, Guillermo J.
Ruiz, Gustavo Teodosio
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv NORHARMANE – TD-DFT
PHOTOCHEMISTRY
PHOTOPHYSICS
PULSE RADIOLYSIS
RHENIUM TRICARBONYL COMPLEXES
SINGLET OXYGEN GENERATION
topic NORHARMANE – TD-DFT
PHOTOCHEMISTRY
PHOTOPHYSICS
PULSE RADIOLYSIS
RHENIUM TRICARBONYL COMPLEXES
SINGLET OXYGEN GENERATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The photochemical and photophysical properties of a Re(I) tricarbonyl complex, ClRe(CO)3(nHo)2, where nHo = 9H-pyrido[3,4-b] indole (norharmane), were investigated in solution phase by a combination of steady state emission spectroscopy, laser flash photolysis (LFP) and pulse radiolysis (PR) techniques. These results allowed us to identify and study the reactivity of the β-carboline (nHo) Rhenium(I) complex main excited states. The absorption spectrum as well as the steady-state and time-resolved luminescence of the complex exhibits a marked dependence with the solvent properties. These experimentally observed results were corroborated by quantum chemical calculations, TD-DFT. The most important electronic transitions present in the spectrum in all solvents are MLLCTRe(CO)3→nHo1, nHo2 along with a mixture of ILnHo and LLCTCl→nHo transitions. The relationship between the dipole moment and the polarity of the solvent was rationalized in terms of the electron density inside and outside the complex. While the luminescence of the complex is mainly attributed to the emitting 1ILnHo state, in LFP experiments a MLCT excited state was also detected. The species generated in either reductive or oxidative conditions in LFP experiments were compared with those obtained in PR. Also, the quenching rate constant (kq) of the excited state with MV+2 was calculated. The excited state of the complex can efficiently generate singlet oxygen in acetonitrile yielding a ΦΔ = 0.25 ± 0.02. Optoacoustic measurements showed that, after photonic excitation, almost all the absorbed energy by the complex is released to the medium as prompt heat. The investigated photophysical and photochemical properties of ClRe(CO)3(nHo)2 are of significant importance in relation to the use of this β-carboline Rhenium(I) complex in several biomedical fields, such as photodynamic therapy and photoactivated chemotherapy as well as new alternative therapies such as regional hyperthermia.
Fil: Maisuls, Iván. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina
Fil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Fil: David Gara, Pedro Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones Ópticas. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones Ópticas. Universidad Nacional de La Plata. Centro de Investigaciones Ópticas; Argentina
Fil: Cabrerizo, Franco Martín. Universidad Nacional de San Martin. Instituto Tecnologico de Chascomus. - Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - la Plata. Instituto Tecnologico de Chascomus.; Argentina
Fil: Ferraudi, Guillermo J.. University of Notre Dame; Estados Unidos
Fil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description The photochemical and photophysical properties of a Re(I) tricarbonyl complex, ClRe(CO)3(nHo)2, where nHo = 9H-pyrido[3,4-b] indole (norharmane), were investigated in solution phase by a combination of steady state emission spectroscopy, laser flash photolysis (LFP) and pulse radiolysis (PR) techniques. These results allowed us to identify and study the reactivity of the β-carboline (nHo) Rhenium(I) complex main excited states. The absorption spectrum as well as the steady-state and time-resolved luminescence of the complex exhibits a marked dependence with the solvent properties. These experimentally observed results were corroborated by quantum chemical calculations, TD-DFT. The most important electronic transitions present in the spectrum in all solvents are MLLCTRe(CO)3→nHo1, nHo2 along with a mixture of ILnHo and LLCTCl→nHo transitions. The relationship between the dipole moment and the polarity of the solvent was rationalized in terms of the electron density inside and outside the complex. While the luminescence of the complex is mainly attributed to the emitting 1ILnHo state, in LFP experiments a MLCT excited state was also detected. The species generated in either reductive or oxidative conditions in LFP experiments were compared with those obtained in PR. Also, the quenching rate constant (kq) of the excited state with MV+2 was calculated. The excited state of the complex can efficiently generate singlet oxygen in acetonitrile yielding a ΦΔ = 0.25 ± 0.02. Optoacoustic measurements showed that, after photonic excitation, almost all the absorbed energy by the complex is released to the medium as prompt heat. The investigated photophysical and photochemical properties of ClRe(CO)3(nHo)2 are of significant importance in relation to the use of this β-carboline Rhenium(I) complex in several biomedical fields, such as photodynamic therapy and photoactivated chemotherapy as well as new alternative therapies such as regional hyperthermia.
publishDate 2021
dc.date.none.fl_str_mv 2021-12
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/11336/164152
Maisuls, Iván; Wolcan, Ezequiel; David Gara, Pedro Maximiliano; Cabrerizo, Franco Martín; Ferraudi, Guillermo J.; et al.; Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity; Elsevier; Journal of Photochemistry and Photobiology; 8; 100078; 12-2021; 1-10
2666-4690
CONICET Digital
CONICET
url http://hdl.handle.net/11336/164152
identifier_str_mv Maisuls, Iván; Wolcan, Ezequiel; David Gara, Pedro Maximiliano; Cabrerizo, Franco Martín; Ferraudi, Guillermo J.; et al.; Photophysical properties of a β-Carboline Rhenium (I) complex. Solvent effects on excited states and their redox reactivity; Elsevier; Journal of Photochemistry and Photobiology; 8; 100078; 12-2021; 1-10
2666-4690
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://linkinghub.elsevier.com/retrieve/pii/S2666469021000634
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jpap.2021.100078
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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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score 13.070432

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