Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes

Autores
Caraballo, Rolando Manuel; Rosi, Pablo Eduardo; Hodak, Jose Hector; Baraldo Victorica, Luis Mario
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report the photophysical and photochemical properties of RuII–polypyridine complexes [Ru(bpy)(dcbpy)py2]2+ (1)2+ and [Ru(dcbpy)2py2]2+ (2)2+ (bpy = 2,2′-bipyridine, dcbpy = 4,4′-dicarboxy-2,2′-bipyridine, py = pyridine). These complexes combine a monodentate ligand with a chelate bipyridine substituted with carboxylate groups. At low pH, both complexes present metal-to-ligand charge transfer absorption bands in the visible region and room-temperature photoluminescence with long excited-state lifetimes (τ > 200 ns). At physiological pH, their absorption and emission maxima are displaced to higher energies, with a significant reduction of their emission lifetime. These species show photosubstitution of the monodentate pyridine upon irradiation at 450 nm. At low pH, the quantum yield for this process is very low, but at physiological pH, they are very active, with a φPS,450 value of 0.14 for (1)2+ and of 0.17 for (2)2+. The products of photosubstitution were identified as monoaquo complexes. Both the reactants and the products of the photosubstitution show photoluminescence, but with very different lifetimes, making it possible to monitor the reaction by the time constant of their decay. The ability of complexes (1)2+ and (2)2+ to photorelease monodentate ligands at physiological pH makes them attractive candidates for the delivery of biomolecules linked to more complex structures through the carboxylate functional group.
Fil: Caraballo, Rolando Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Rosi, Pablo Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Materia
Carboxylate Ligands
Photochemistry
Photosubstitution
Ruthenium
Temperature-Dependent Quantum Yield
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:11336/65210
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/65210
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine ComplexesCaraballo, Rolando ManuelRosi, Pablo EduardoHodak, Jose HectorBaraldo Victorica, Luis MarioCarboxylate LigandsPhotochemistryPhotosubstitutionRutheniumTemperature-Dependent Quantum Yieldhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report the photophysical and photochemical properties of RuII–polypyridine complexes [Ru(bpy)(dcbpy)py2]2+ (1)2+ and [Ru(dcbpy)2py2]2+ (2)2+ (bpy = 2,2′-bipyridine, dcbpy = 4,4′-dicarboxy-2,2′-bipyridine, py = pyridine). These complexes combine a monodentate ligand with a chelate bipyridine substituted with carboxylate groups. At low pH, both complexes present metal-to-ligand charge transfer absorption bands in the visible region and room-temperature photoluminescence with long excited-state lifetimes (τ > 200 ns). At physiological pH, their absorption and emission maxima are displaced to higher energies, with a significant reduction of their emission lifetime. These species show photosubstitution of the monodentate pyridine upon irradiation at 450 nm. At low pH, the quantum yield for this process is very low, but at physiological pH, they are very active, with a φPS,450 value of 0.14 for (1)2+ and of 0.17 for (2)2+. The products of photosubstitution were identified as monoaquo complexes. Both the reactants and the products of the photosubstitution show photoluminescence, but with very different lifetimes, making it possible to monitor the reaction by the time constant of their decay. The ability of complexes (1)2+ and (2)2+ to photorelease monodentate ligands at physiological pH makes them attractive candidates for the delivery of biomolecules linked to more complex structures through the carboxylate functional group.Fil: Caraballo, Rolando Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Rosi, Pablo Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaWiley VCH Verlag2017-08info: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/11336/65210Caraballo, Rolando Manuel; Rosi, Pablo Eduardo; Hodak, Jose Hector; Baraldo Victorica, Luis Mario; Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes; Wiley VCH Verlag; European Journal of Inorganic Chemistry; 2017; 30; 8-2017; 3612-36211434-1948CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://doi.wiley.com/10.1002/ejic.201700439info:eu-repo/semantics/altIdentifier/doi/10.1002/ejic.201700439info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:16:09Zoai:ri.conicet.gov.ar:11336/65210instacron: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 11:16:09.474CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes
title Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes
spellingShingle Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes
Caraballo, Rolando Manuel
Carboxylate Ligands
Photochemistry
Photosubstitution
Ruthenium
Temperature-Dependent Quantum Yield
title_short Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes
title_full Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes
title_fullStr Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes
title_full_unstemmed Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes
title_sort Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes
dc.creator.none.fl_str_mv Caraballo, Rolando Manuel
Rosi, Pablo Eduardo
Hodak, Jose Hector
Baraldo Victorica, Luis Mario
author Caraballo, Rolando Manuel
author_facet Caraballo, Rolando Manuel
Rosi, Pablo Eduardo
Hodak, Jose Hector
Baraldo Victorica, Luis Mario
author_role author
author2 Rosi, Pablo Eduardo
Hodak, Jose Hector
Baraldo Victorica, Luis Mario
author2_role author
author
author
dc.subject.none.fl_str_mv Carboxylate Ligands
Photochemistry
Photosubstitution
Ruthenium
Temperature-Dependent Quantum Yield
topic Carboxylate Ligands
Photochemistry
Photosubstitution
Ruthenium
Temperature-Dependent Quantum Yield
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report the photophysical and photochemical properties of RuII–polypyridine complexes [Ru(bpy)(dcbpy)py2]2+ (1)2+ and [Ru(dcbpy)2py2]2+ (2)2+ (bpy = 2,2′-bipyridine, dcbpy = 4,4′-dicarboxy-2,2′-bipyridine, py = pyridine). These complexes combine a monodentate ligand with a chelate bipyridine substituted with carboxylate groups. At low pH, both complexes present metal-to-ligand charge transfer absorption bands in the visible region and room-temperature photoluminescence with long excited-state lifetimes (τ > 200 ns). At physiological pH, their absorption and emission maxima are displaced to higher energies, with a significant reduction of their emission lifetime. These species show photosubstitution of the monodentate pyridine upon irradiation at 450 nm. At low pH, the quantum yield for this process is very low, but at physiological pH, they are very active, with a φPS,450 value of 0.14 for (1)2+ and of 0.17 for (2)2+. The products of photosubstitution were identified as monoaquo complexes. Both the reactants and the products of the photosubstitution show photoluminescence, but with very different lifetimes, making it possible to monitor the reaction by the time constant of their decay. The ability of complexes (1)2+ and (2)2+ to photorelease monodentate ligands at physiological pH makes them attractive candidates for the delivery of biomolecules linked to more complex structures through the carboxylate functional group.
Fil: Caraballo, Rolando Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Rosi, Pablo Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Hodak, Jose Hector. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Baraldo Victorica, Luis Mario. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
description We report the photophysical and photochemical properties of RuII–polypyridine complexes [Ru(bpy)(dcbpy)py2]2+ (1)2+ and [Ru(dcbpy)2py2]2+ (2)2+ (bpy = 2,2′-bipyridine, dcbpy = 4,4′-dicarboxy-2,2′-bipyridine, py = pyridine). These complexes combine a monodentate ligand with a chelate bipyridine substituted with carboxylate groups. At low pH, both complexes present metal-to-ligand charge transfer absorption bands in the visible region and room-temperature photoluminescence with long excited-state lifetimes (τ > 200 ns). At physiological pH, their absorption and emission maxima are displaced to higher energies, with a significant reduction of their emission lifetime. These species show photosubstitution of the monodentate pyridine upon irradiation at 450 nm. At low pH, the quantum yield for this process is very low, but at physiological pH, they are very active, with a φPS,450 value of 0.14 for (1)2+ and of 0.17 for (2)2+. The products of photosubstitution were identified as monoaquo complexes. Both the reactants and the products of the photosubstitution show photoluminescence, but with very different lifetimes, making it possible to monitor the reaction by the time constant of their decay. The ability of complexes (1)2+ and (2)2+ to photorelease monodentate ligands at physiological pH makes them attractive candidates for the delivery of biomolecules linked to more complex structures through the carboxylate functional group.
publishDate 2017
dc.date.none.fl_str_mv 2017-08
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/11336/65210
Caraballo, Rolando Manuel; Rosi, Pablo Eduardo; Hodak, Jose Hector; Baraldo Victorica, Luis Mario; Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes; Wiley VCH Verlag; European Journal of Inorganic Chemistry; 2017; 30; 8-2017; 3612-3621
1434-1948
CONICET Digital
CONICET
url http://hdl.handle.net/11336/65210
identifier_str_mv Caraballo, Rolando Manuel; Rosi, Pablo Eduardo; Hodak, Jose Hector; Baraldo Victorica, Luis Mario; Photosubstitution of Monodentate Ligands from RuII–Dicarboxybipyridine Complexes; Wiley VCH Verlag; European Journal of Inorganic Chemistry; 2017; 30; 8-2017; 3612-3621
1434-1948
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://doi.wiley.com/10.1002/ejic.201700439
info:eu-repo/semantics/altIdentifier/doi/10.1002/ejic.201700439
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 Wiley VCH Verlag
publisher.none.fl_str_mv Wiley VCH Verlag
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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