Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers

Autores
Rossi, Melina Brenda; Alborés, Pablo; Baraldo Victorica, Luis Mario
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be adjusted smoothly by changing the acceptor properties of the solvent and the σ donor properties of the L′ pyridine ligand. In solution these complexes exhibit an intense solvent-dependent MM′CT (RuII → FeIII) absorption in the near infrared region. Analysis of this band in different complexes and solvents suggests an enhanced interaction as the energies of the metal centers come closer. From this trend the anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]- (dmap = 4-dimethylaminopyridine) in water is expected to belong to the class II-III, but its spectral properties indicates a ground state with Ru(III)-Fe(II) character. The stabilization of this electronic isomer is probably related to the better donor properties of the hexacyanoferrate(II) moiety and its stronger interaction with water.
Fil: Rossi, Melina Brenda. 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: Alborés, Pablo. 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: 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
Materia
Cyanide Bridged Complexes
Intervalence Charge Transfer
Metal-Metal Interaction
Mixed Valence Complexes
Solvent Effect
Spectroelectrochemistry
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:11336/68412
Acceder
id CONICETDig_a22c8934ecdac3855ffa3669d53182e6
oai_identifier_str oai:ri.conicet.gov.ar:11336/68412
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomersRossi, Melina BrendaAlborés, PabloBaraldo Victorica, Luis MarioCyanide Bridged ComplexesIntervalence Charge TransferMetal-Metal InteractionMixed Valence ComplexesSolvent EffectSpectroelectrochemistryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be adjusted smoothly by changing the acceptor properties of the solvent and the σ donor properties of the L′ pyridine ligand. In solution these complexes exhibit an intense solvent-dependent MM′CT (RuII → FeIII) absorption in the near infrared region. Analysis of this band in different complexes and solvents suggests an enhanced interaction as the energies of the metal centers come closer. From this trend the anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]- (dmap = 4-dimethylaminopyridine) in water is expected to belong to the class II-III, but its spectral properties indicates a ground state with Ru(III)-Fe(II) character. The stabilization of this electronic isomer is probably related to the better donor properties of the hexacyanoferrate(II) moiety and its stronger interaction with water.Fil: Rossi, Melina Brenda. 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: Alborés, Pablo. 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: 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; ArgentinaElsevier Science Sa2011-08info: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/11336/68412Rossi, Melina Brenda; Alborés, Pablo; Baraldo Victorica, Luis Mario; Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers; Elsevier Science Sa; Inorganica Chimica Acta; 374; 1; 8-2011; 334-3400020-1693CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S0020169311002878info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ica.2011.03.032info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:38:15Zoai:ri.conicet.gov.ar:11336/68412instacron: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 10:38:16.139CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
title Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
spellingShingle Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
Rossi, Melina Brenda
Cyanide Bridged Complexes
Intervalence Charge Transfer
Metal-Metal Interaction
Mixed Valence Complexes
Solvent Effect
Spectroelectrochemistry
title_short Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
title_full Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
title_fullStr Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
title_full_unstemmed Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
title_sort Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers
dc.creator.none.fl_str_mv Rossi, Melina Brenda
Alborés, Pablo
Baraldo Victorica, Luis Mario
author Rossi, Melina Brenda
author_facet Rossi, Melina Brenda
Alborés, Pablo
Baraldo Victorica, Luis Mario
author_role author
author2 Alborés, Pablo
Baraldo Victorica, Luis Mario
author2_role author
author
dc.subject.none.fl_str_mv Cyanide Bridged Complexes
Intervalence Charge Transfer
Metal-Metal Interaction
Mixed Valence Complexes
Solvent Effect
Spectroelectrochemistry
topic Cyanide Bridged Complexes
Intervalence Charge Transfer
Metal-Metal Interaction
Mixed Valence Complexes
Solvent Effect
Spectroelectrochemistry
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 here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be adjusted smoothly by changing the acceptor properties of the solvent and the σ donor properties of the L′ pyridine ligand. In solution these complexes exhibit an intense solvent-dependent MM′CT (RuII → FeIII) absorption in the near infrared region. Analysis of this band in different complexes and solvents suggests an enhanced interaction as the energies of the metal centers come closer. From this trend the anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]- (dmap = 4-dimethylaminopyridine) in water is expected to belong to the class II-III, but its spectral properties indicates a ground state with Ru(III)-Fe(II) character. The stabilization of this electronic isomer is probably related to the better donor properties of the hexacyanoferrate(II) moiety and its stronger interaction with water.
Fil: Rossi, Melina Brenda. 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: Alborés, Pablo. 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: 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
description We report here the synthesis and properties of a family of mixed-valence cyanide-bridged dinuclear complex ions trans-[(L′L4Ru II(μ-NC)FeIII(CN)5]- (with L = pyridine or 4-dimethylaminopyridine (dmap) and L′ = pyridine, 4-methoxypyridine (meopy) or 4-dimethylaminopyridine)) whose properties could be adjusted smoothly by changing the acceptor properties of the solvent and the σ donor properties of the L′ pyridine ligand. In solution these complexes exhibit an intense solvent-dependent MM′CT (RuII → FeIII) absorption in the near infrared region. Analysis of this band in different complexes and solvents suggests an enhanced interaction as the energies of the metal centers come closer. From this trend the anion trans-[(dmap)5Ru(μ-NC)Fe(CN)5]- (dmap = 4-dimethylaminopyridine) in water is expected to belong to the class II-III, but its spectral properties indicates a ground state with Ru(III)-Fe(II) character. The stabilization of this electronic isomer is probably related to the better donor properties of the hexacyanoferrate(II) moiety and its stronger interaction with water.
publishDate 2011
dc.date.none.fl_str_mv 2011-08
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/11336/68412
Rossi, Melina Brenda; Alborés, Pablo; Baraldo Victorica, Luis Mario; Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers; Elsevier Science Sa; Inorganica Chimica Acta; 374; 1; 8-2011; 334-340
0020-1693
CONICET Digital
CONICET
url http://hdl.handle.net/11336/68412
identifier_str_mv Rossi, Melina Brenda; Alborés, Pablo; Baraldo Victorica, Luis Mario; Exploring the properties of mixed valence cyanide bridged dinuclear complexes: Solvent stabilization of electronic isomers; Elsevier Science Sa; Inorganica Chimica Acta; 374; 1; 8-2011; 334-340
0020-1693
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://www.sciencedirect.com/science/article/pii/S0020169311002878
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ica.2011.03.032
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 Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
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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