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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/65210
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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 Técnicas2025-09-29T09:47:16Zoai: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:34982025-09-29 09:47:17.171CONICET 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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1844613473668956160 |
score |
13.070432 |