New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium

Autores
Mellace, Maria G.; Fagalde, Florencia; Katz, Néstor Eduardo
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
wo new mixed-metal mixed-valent complexes, of formulae: [(CO)3(bpy)ReI(bpe)RuIII(NH3)5]4+ and [(CO)3(bpy)ReI(4-CNpy)RuIII(NH3)5]4+ (where bpy=2,2′-bipyridine, bpe=trans-1,2-bis(4-pyridil)ethene, 4-CNpy=4-cyanopyridine), were prepared and characterized as solids and in acetonitrile solutions. From their spectroscopic, electrochemical and photophysical properties, the values for the reorganization energies λ and electronic coupling elements HAB for the metal-to-metal intramolecular electron transfers mediated by the N-heterocyclic bridges were calculated, using the Marcus–Hush formalism. For the 4-CNpy derivative, the reverse ruthenium-to-rhenium charge recombination—that should follow light excitation—is expected to be in the normal region, while for the bpe derivative this reaction is predicted to lie in the inverted region. The differences in redox potentials and in λ for both species account for these changes, which are relevant in the design of efficient photoconverters.
Fil: Mellace, Maria G.. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; Argentina
Fil: Fagalde, Florencia. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina
Fil: Katz, Néstor Eduardo. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina
Materia
Mixed-Valent
Ruthenium Complexes
Rhenium Complexes
Intramolecular Electron Transfer
Energy Conversion
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:11336/6936
Acceder
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repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and rutheniumMellace, Maria G.Fagalde, FlorenciaKatz, Néstor EduardoMixed-ValentRuthenium ComplexesRhenium ComplexesIntramolecular Electron TransferEnergy Conversionhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1wo new mixed-metal mixed-valent complexes, of formulae: [(CO)3(bpy)ReI(bpe)RuIII(NH3)5]4+ and [(CO)3(bpy)ReI(4-CNpy)RuIII(NH3)5]4+ (where bpy=2,2′-bipyridine, bpe=trans-1,2-bis(4-pyridil)ethene, 4-CNpy=4-cyanopyridine), were prepared and characterized as solids and in acetonitrile solutions. From their spectroscopic, electrochemical and photophysical properties, the values for the reorganization energies λ and electronic coupling elements HAB for the metal-to-metal intramolecular electron transfers mediated by the N-heterocyclic bridges were calculated, using the Marcus–Hush formalism. For the 4-CNpy derivative, the reverse ruthenium-to-rhenium charge recombination—that should follow light excitation—is expected to be in the normal region, while for the bpe derivative this reaction is predicted to lie in the inverted region. The differences in redox potentials and in λ for both species account for these changes, which are relevant in the design of efficient photoconverters.Fil: Mellace, Maria G.. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; ArgentinaFil: Fagalde, Florencia. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; ArgentinaFil: Katz, Néstor Eduardo. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; ArgentinaElsevier2013-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/6936Mellace, Maria G.; Fagalde, Florencia; Katz, Néstor Eduardo; New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium; Elsevier; Polyhedron; 22; 3; 12-2013; 369-3740277-5387enginfo:eu-repo/semantics/altIdentifier/doi/10.1016/S0277-5387(02)01371-2info:eu-repo/semantics/altIdentifier/doi/info:eu-repo/semantics/altIdentifier/ark/http://www.sciencedirect.com/science/article/pii/S0277538702013712info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:12:23Zoai:ri.conicet.gov.ar:11336/6936instacron: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:34982025-09-10 13:12:23.871CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium
title New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium
spellingShingle New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium
Mellace, Maria G.
Mixed-Valent
Ruthenium Complexes
Rhenium Complexes
Intramolecular Electron Transfer
Energy Conversion
title_short New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium
title_full New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium
title_fullStr New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium
title_full_unstemmed New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium
title_sort New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium
dc.creator.none.fl_str_mv Mellace, Maria G.
Fagalde, Florencia
Katz, Néstor Eduardo
author Mellace, Maria G.
author_facet Mellace, Maria G.
Fagalde, Florencia
Katz, Néstor Eduardo
author_role author
author2 Fagalde, Florencia
Katz, Néstor Eduardo
author2_role author
author
dc.subject.none.fl_str_mv Mixed-Valent
Ruthenium Complexes
Rhenium Complexes
Intramolecular Electron Transfer
Energy Conversion
topic Mixed-Valent
Ruthenium Complexes
Rhenium Complexes
Intramolecular Electron Transfer
Energy Conversion
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv wo new mixed-metal mixed-valent complexes, of formulae: [(CO)3(bpy)ReI(bpe)RuIII(NH3)5]4+ and [(CO)3(bpy)ReI(4-CNpy)RuIII(NH3)5]4+ (where bpy=2,2′-bipyridine, bpe=trans-1,2-bis(4-pyridil)ethene, 4-CNpy=4-cyanopyridine), were prepared and characterized as solids and in acetonitrile solutions. From their spectroscopic, electrochemical and photophysical properties, the values for the reorganization energies λ and electronic coupling elements HAB for the metal-to-metal intramolecular electron transfers mediated by the N-heterocyclic bridges were calculated, using the Marcus–Hush formalism. For the 4-CNpy derivative, the reverse ruthenium-to-rhenium charge recombination—that should follow light excitation—is expected to be in the normal region, while for the bpe derivative this reaction is predicted to lie in the inverted region. The differences in redox potentials and in λ for both species account for these changes, which are relevant in the design of efficient photoconverters.
Fil: Mellace, Maria G.. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; Argentina
Fil: Fagalde, Florencia. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina
Fil: Katz, Néstor Eduardo. Universidad Nacional de Tucuman. Facultad de Bioquimica, Quimica y Farmacia. Instituto de Quimica Fisica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Tucumán. Instituto de Quimica del Noroeste; Argentina
description wo new mixed-metal mixed-valent complexes, of formulae: [(CO)3(bpy)ReI(bpe)RuIII(NH3)5]4+ and [(CO)3(bpy)ReI(4-CNpy)RuIII(NH3)5]4+ (where bpy=2,2′-bipyridine, bpe=trans-1,2-bis(4-pyridil)ethene, 4-CNpy=4-cyanopyridine), were prepared and characterized as solids and in acetonitrile solutions. From their spectroscopic, electrochemical and photophysical properties, the values for the reorganization energies λ and electronic coupling elements HAB for the metal-to-metal intramolecular electron transfers mediated by the N-heterocyclic bridges were calculated, using the Marcus–Hush formalism. For the 4-CNpy derivative, the reverse ruthenium-to-rhenium charge recombination—that should follow light excitation—is expected to be in the normal region, while for the bpe derivative this reaction is predicted to lie in the inverted region. The differences in redox potentials and in λ for both species account for these changes, which are relevant in the design of efficient photoconverters.
publishDate 2013
dc.date.none.fl_str_mv 2013-12
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/11336/6936
Mellace, Maria G.; Fagalde, Florencia; Katz, Néstor Eduardo; New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium; Elsevier; Polyhedron; 22; 3; 12-2013; 369-374
0277-5387
url http://hdl.handle.net/11336/6936
identifier_str_mv Mellace, Maria G.; Fagalde, Florencia; Katz, Néstor Eduardo; New asymmetric N-heterocyclic-bridged mixed-valent dinuclear complexes of rhenium and ruthenium; Elsevier; Polyhedron; 22; 3; 12-2013; 369-374
0277-5387
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/S0277-5387(02)01371-2
info:eu-repo/semantics/altIdentifier/doi/
info:eu-repo/semantics/altIdentifier/ark/http://www.sciencedirect.com/science/article/pii/S0277538702013712
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
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)
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 12.993085

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