Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes

Autores
Ramirez, Cristina Lujan; Pegoraro, César Nicolás; Filevich, Oscar; Bruttomesso, Andrea; Etchenique, Roberto Argentino; Parise, Alejandro Ruben
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We describe in this paper the properties of [RuII/III(bpy)2ClL]+1/+2 and [RuII/III(bpy)2L2]+2/+3. L = ditolyl-3-pyridylamine (dt3pya) is a redox active ligand related to triarylamines, which is very similar to 3-aminopyridine except for the reversible redox behavior. The monosubstituted complex shows a metal-to-ligand charge-transfer (MLCT) at 502 nm, and reversible waves in acetonitrile at E0(RuIII/II) = 1.07 V, E0(L+/0) = 1.46 V (NHE). The disubstituted complex shows an MLCT at 461 nm, a photorelease of dt3pya with quantum yield of 0.11 at 473 nm, and two reversible one-electron overlapped waves at 1.39 V associated with one of the ligands (1.37 V) and RuIII/II (1.41 V). Further oxidation of the second ligand at 1.80 V forms a 2,2′-bipiridine derivative, in an irreversible reaction similar to dimerization of triphenylamine to yield tetraphenylbenzidine. In the dioxidized state, the spectroelectrochemistry of the disubstituted complex shows a ligand-to-ligand charge transfer at 1425 nm, with a transition moment of 1.25 Å and an effective two-state coupling of 1200 cm–1. No charge transfer between ligands was observed when Ru was in a 2+ oxidation state. We propose that a superexchange process would be involved in ligand–metal–ligand charge transfer, when ligands and metals are engaged in complementary π interactions, as in metal–ligand–metal complexes. Best orbital matching occurs when metallic donor fragments are combined with acceptor ligands and vice versa. In our case, RuIII bridge (an acceptor) and two dt3pya (donors, one of them being oxidized) made the complex a Robin–Day Class II system, while the RuII bridge (a donor, reduced) was not able to couple two dt3pya (also donors, one oxidized).
Fil: Ramirez, Cristina Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina
Fil: Pegoraro, César Nicolás. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina
Fil: Filevich, Oscar. 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
Fil: Bruttomesso, Andrea. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina
Fil: Etchenique, Roberto Argentino. 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
Fil: Parise, Alejandro Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina
Materia
RUTHENIUM
TRIPHENILAMINE
LIGAND TO LIGAND CHANGE TRANSFER
METAL TO LIGAND CHANGE TRANSFER
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:11336/102641
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/102641
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer ProcessesRamirez, Cristina LujanPegoraro, César NicolásFilevich, OscarBruttomesso, AndreaEtchenique, Roberto ArgentinoParise, Alejandro RubenRUTHENIUMTRIPHENILAMINELIGAND TO LIGAND CHANGE TRANSFERMETAL TO LIGAND CHANGE TRANSFERhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We describe in this paper the properties of [RuII/III(bpy)2ClL]+1/+2 and [RuII/III(bpy)2L2]+2/+3. L = ditolyl-3-pyridylamine (dt3pya) is a redox active ligand related to triarylamines, which is very similar to 3-aminopyridine except for the reversible redox behavior. The monosubstituted complex shows a metal-to-ligand charge-transfer (MLCT) at 502 nm, and reversible waves in acetonitrile at E0(RuIII/II) = 1.07 V, E0(L+/0) = 1.46 V (NHE). The disubstituted complex shows an MLCT at 461 nm, a photorelease of dt3pya with quantum yield of 0.11 at 473 nm, and two reversible one-electron overlapped waves at 1.39 V associated with one of the ligands (1.37 V) and RuIII/II (1.41 V). Further oxidation of the second ligand at 1.80 V forms a 2,2′-bipiridine derivative, in an irreversible reaction similar to dimerization of triphenylamine to yield tetraphenylbenzidine. In the dioxidized state, the spectroelectrochemistry of the disubstituted complex shows a ligand-to-ligand charge transfer at 1425 nm, with a transition moment of 1.25 Å and an effective two-state coupling of 1200 cm–1. No charge transfer between ligands was observed when Ru was in a 2+ oxidation state. We propose that a superexchange process would be involved in ligand–metal–ligand charge transfer, when ligands and metals are engaged in complementary π interactions, as in metal–ligand–metal complexes. Best orbital matching occurs when metallic donor fragments are combined with acceptor ligands and vice versa. In our case, RuIII bridge (an acceptor) and two dt3pya (donors, one of them being oxidized) made the complex a Robin–Day Class II system, while the RuII bridge (a donor, reduced) was not able to couple two dt3pya (also donors, one oxidized).Fil: Ramirez, Cristina Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; ArgentinaFil: Pegoraro, César Nicolás. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaFil: Filevich, Oscar. 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; ArgentinaFil: Bruttomesso, Andrea. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; ArgentinaFil: Etchenique, Roberto Argentino. 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; ArgentinaFil: Parise, Alejandro Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; ArgentinaAmerican Chemical Society2012-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/102641Ramirez, Cristina Lujan; Pegoraro, César Nicolás; Filevich, Oscar; Bruttomesso, Andrea; Etchenique, Roberto Argentino; et al.; Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes; American Chemical Society; Inorganic Chemistry; 51; 1-2012; 1261-12680020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ic200966finfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic200966finfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:25:09Zoai:ri.conicet.gov.ar:11336/102641instacron: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 10:25:10.113CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes
title Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes
spellingShingle Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes
Ramirez, Cristina Lujan
RUTHENIUM
TRIPHENILAMINE
LIGAND TO LIGAND CHANGE TRANSFER
METAL TO LIGAND CHANGE TRANSFER
title_short Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes
title_full Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes
title_fullStr Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes
title_full_unstemmed Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes
title_sort Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes
dc.creator.none.fl_str_mv Ramirez, Cristina Lujan
Pegoraro, César Nicolás
Filevich, Oscar
Bruttomesso, Andrea
Etchenique, Roberto Argentino
Parise, Alejandro Ruben
author Ramirez, Cristina Lujan
author_facet Ramirez, Cristina Lujan
Pegoraro, César Nicolás
Filevich, Oscar
Bruttomesso, Andrea
Etchenique, Roberto Argentino
Parise, Alejandro Ruben
author_role author
author2 Pegoraro, César Nicolás
Filevich, Oscar
Bruttomesso, Andrea
Etchenique, Roberto Argentino
Parise, Alejandro Ruben
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv RUTHENIUM
TRIPHENILAMINE
LIGAND TO LIGAND CHANGE TRANSFER
METAL TO LIGAND CHANGE TRANSFER
topic RUTHENIUM
TRIPHENILAMINE
LIGAND TO LIGAND CHANGE TRANSFER
METAL TO LIGAND CHANGE TRANSFER
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 describe in this paper the properties of [RuII/III(bpy)2ClL]+1/+2 and [RuII/III(bpy)2L2]+2/+3. L = ditolyl-3-pyridylamine (dt3pya) is a redox active ligand related to triarylamines, which is very similar to 3-aminopyridine except for the reversible redox behavior. The monosubstituted complex shows a metal-to-ligand charge-transfer (MLCT) at 502 nm, and reversible waves in acetonitrile at E0(RuIII/II) = 1.07 V, E0(L+/0) = 1.46 V (NHE). The disubstituted complex shows an MLCT at 461 nm, a photorelease of dt3pya with quantum yield of 0.11 at 473 nm, and two reversible one-electron overlapped waves at 1.39 V associated with one of the ligands (1.37 V) and RuIII/II (1.41 V). Further oxidation of the second ligand at 1.80 V forms a 2,2′-bipiridine derivative, in an irreversible reaction similar to dimerization of triphenylamine to yield tetraphenylbenzidine. In the dioxidized state, the spectroelectrochemistry of the disubstituted complex shows a ligand-to-ligand charge transfer at 1425 nm, with a transition moment of 1.25 Å and an effective two-state coupling of 1200 cm–1. No charge transfer between ligands was observed when Ru was in a 2+ oxidation state. We propose that a superexchange process would be involved in ligand–metal–ligand charge transfer, when ligands and metals are engaged in complementary π interactions, as in metal–ligand–metal complexes. Best orbital matching occurs when metallic donor fragments are combined with acceptor ligands and vice versa. In our case, RuIII bridge (an acceptor) and two dt3pya (donors, one of them being oxidized) made the complex a Robin–Day Class II system, while the RuII bridge (a donor, reduced) was not able to couple two dt3pya (also donors, one oxidized).
Fil: Ramirez, Cristina Lujan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina
Fil: Pegoraro, César Nicolás. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina
Fil: Filevich, Oscar. 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
Fil: Bruttomesso, Andrea. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Orgánica; Argentina
Fil: Etchenique, Roberto Argentino. 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
Fil: Parise, Alejandro Ruben. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina
description We describe in this paper the properties of [RuII/III(bpy)2ClL]+1/+2 and [RuII/III(bpy)2L2]+2/+3. L = ditolyl-3-pyridylamine (dt3pya) is a redox active ligand related to triarylamines, which is very similar to 3-aminopyridine except for the reversible redox behavior. The monosubstituted complex shows a metal-to-ligand charge-transfer (MLCT) at 502 nm, and reversible waves in acetonitrile at E0(RuIII/II) = 1.07 V, E0(L+/0) = 1.46 V (NHE). The disubstituted complex shows an MLCT at 461 nm, a photorelease of dt3pya with quantum yield of 0.11 at 473 nm, and two reversible one-electron overlapped waves at 1.39 V associated with one of the ligands (1.37 V) and RuIII/II (1.41 V). Further oxidation of the second ligand at 1.80 V forms a 2,2′-bipiridine derivative, in an irreversible reaction similar to dimerization of triphenylamine to yield tetraphenylbenzidine. In the dioxidized state, the spectroelectrochemistry of the disubstituted complex shows a ligand-to-ligand charge transfer at 1425 nm, with a transition moment of 1.25 Å and an effective two-state coupling of 1200 cm–1. No charge transfer between ligands was observed when Ru was in a 2+ oxidation state. We propose that a superexchange process would be involved in ligand–metal–ligand charge transfer, when ligands and metals are engaged in complementary π interactions, as in metal–ligand–metal complexes. Best orbital matching occurs when metallic donor fragments are combined with acceptor ligands and vice versa. In our case, RuIII bridge (an acceptor) and two dt3pya (donors, one of them being oxidized) made the complex a Robin–Day Class II system, while the RuII bridge (a donor, reduced) was not able to couple two dt3pya (also donors, one oxidized).
publishDate 2012
dc.date.none.fl_str_mv 2012-01
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/11336/102641
Ramirez, Cristina Lujan; Pegoraro, César Nicolás; Filevich, Oscar; Bruttomesso, Andrea; Etchenique, Roberto Argentino; et al.; Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes; American Chemical Society; Inorganic Chemistry; 51; 1-2012; 1261-1268
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/102641
identifier_str_mv Ramirez, Cristina Lujan; Pegoraro, César Nicolás; Filevich, Oscar; Bruttomesso, Andrea; Etchenique, Roberto Argentino; et al.; Role of Ruthenium Oxidation States in Ligand-to-Ligand Charge Transfer Processes; American Chemical Society; Inorganic Chemistry; 51; 1-2012; 1261-1268
0020-1669
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://pubs.acs.org/doi/abs/10.1021/ic200966f
info:eu-repo/semantics/altIdentifier/doi/10.1021/ic200966f
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
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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score 13.070432

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