Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy

Autores
Neuman, Nicolás Ignacio; Burna, Emerson Roberto; Baggio, Ricardo Fortunato; Passeggi, Mario Cesar Guillermo; Rizzi, Alberto Claudio; Brondino, Carlos Dante
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report the synthesis and X-ray structure of the dimeric zinc(II) compound [Zn(tda)(phen)]2∙H2tda,(tda = thiodiacetic acid, phen = 1,10-phenanthroline) hereafter Zn(tda)(phen),and a single crystal EPR study of Zn(tda)(phen) doped with Cu(II) ions. Zn(tda)(phen)is isomorphous to its Cu(II) analogue. The EPR spectra show a central signal composed of one to four resonances assigned to Cu-Zn heterodimers, flanked by less intense satellite signals assigned to Cu-Cu homodimers. Analysis of single crystal EPR data allowed us to determine the g- and A-matrices of theCu(II) ion and the anisotropic ZFS parameters of the homodimer. Within the experimental error, the Cu(II) g-matrix obtained for the diluted compound was identical to that previously determinedby us in pure Cu(tda)(phen). The ZFS is shown to be dominated by magnetic dipolar coupling between the unpaired electrons mainly centered around theCu(II) ions, although partially delocalized over the equatorial copper ligands. DFT calculations yielded spin population values compatible with those determined from the analysis of the anisotropic ZFS assuming a distributed dipole model. The information obtained from the diluted compound was used to evaluate the interdimeric exchange interaction between dimeric units in pure Cu(tda)(phen). The comparison between both point and distributed dipole approximations is discussed with reference to the analysis of the EPR data.
Fil: Neuman, Nicolás Ignacio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Burna, Emerson Roberto. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; Argentina
Fil: Passeggi, Mario Cesar Guillermo. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Rizzi, Alberto Claudio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Materia
Zn thiodiacetic acid complex
Cu doped complexes
EPR
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:11336/247818
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/247818
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopyNeuman, Nicolás IgnacioBurna, Emerson RobertoBaggio, Ricardo FortunatoPasseggi, Mario Cesar GuillermoRizzi, Alberto ClaudioBrondino, Carlos DanteZn thiodiacetic acid complexCu doped complexesEPRhttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1We report the synthesis and X-ray structure of the dimeric zinc(II) compound [Zn(tda)(phen)]2∙H2tda,(tda = thiodiacetic acid, phen = 1,10-phenanthroline) hereafter Zn(tda)(phen),and a single crystal EPR study of Zn(tda)(phen) doped with Cu(II) ions. Zn(tda)(phen)is isomorphous to its Cu(II) analogue. The EPR spectra show a central signal composed of one to four resonances assigned to Cu-Zn heterodimers, flanked by less intense satellite signals assigned to Cu-Cu homodimers. Analysis of single crystal EPR data allowed us to determine the g- and A-matrices of theCu(II) ion and the anisotropic ZFS parameters of the homodimer. Within the experimental error, the Cu(II) g-matrix obtained for the diluted compound was identical to that previously determinedby us in pure Cu(tda)(phen). The ZFS is shown to be dominated by magnetic dipolar coupling between the unpaired electrons mainly centered around theCu(II) ions, although partially delocalized over the equatorial copper ligands. DFT calculations yielded spin population values compatible with those determined from the analysis of the anisotropic ZFS assuming a distributed dipole model. The information obtained from the diluted compound was used to evaluate the interdimeric exchange interaction between dimeric units in pure Cu(tda)(phen). The comparison between both point and distributed dipole approximations is discussed with reference to the analysis of the EPR data.Fil: Neuman, Nicolás Ignacio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Burna, Emerson Roberto. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; ArgentinaFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; ArgentinaFil: Passeggi, Mario Cesar Guillermo. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaFil: Rizzi, Alberto Claudio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaFil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; ArgentinaRoyal Society of Chemistry2015-01info: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/11336/247818Neuman, Nicolás Ignacio; Burna, Emerson Roberto; Baggio, Ricardo Fortunato; Passeggi, Mario Cesar Guillermo; Rizzi, Alberto Claudio; et al.; Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy; Royal Society of Chemistry; Inorganic Chemistry Frontiers; 2; 9; 1-2015; 837-8452052-1553CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2015/qi/c5qi00086finfo:eu-repo/semantics/altIdentifier/doi/10.1039/C5QI00086Finfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:31:28Zoai:ri.conicet.gov.ar:11336/247818instacron: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:34982025-10-15 15:31:28.551CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy
title Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy
spellingShingle Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy
Neuman, Nicolás Ignacio
Zn thiodiacetic acid complex
Cu doped complexes
EPR
title_short Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy
title_full Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy
title_fullStr Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy
title_full_unstemmed Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy
title_sort Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy
dc.creator.none.fl_str_mv Neuman, Nicolás Ignacio
Burna, Emerson Roberto
Baggio, Ricardo Fortunato
Passeggi, Mario Cesar Guillermo
Rizzi, Alberto Claudio
Brondino, Carlos Dante
author Neuman, Nicolás Ignacio
author_facet Neuman, Nicolás Ignacio
Burna, Emerson Roberto
Baggio, Ricardo Fortunato
Passeggi, Mario Cesar Guillermo
Rizzi, Alberto Claudio
Brondino, Carlos Dante
author_role author
author2 Burna, Emerson Roberto
Baggio, Ricardo Fortunato
Passeggi, Mario Cesar Guillermo
Rizzi, Alberto Claudio
Brondino, Carlos Dante
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Zn thiodiacetic acid complex
Cu doped complexes
EPR
topic Zn thiodiacetic acid complex
Cu doped complexes
EPR
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report the synthesis and X-ray structure of the dimeric zinc(II) compound [Zn(tda)(phen)]2∙H2tda,(tda = thiodiacetic acid, phen = 1,10-phenanthroline) hereafter Zn(tda)(phen),and a single crystal EPR study of Zn(tda)(phen) doped with Cu(II) ions. Zn(tda)(phen)is isomorphous to its Cu(II) analogue. The EPR spectra show a central signal composed of one to four resonances assigned to Cu-Zn heterodimers, flanked by less intense satellite signals assigned to Cu-Cu homodimers. Analysis of single crystal EPR data allowed us to determine the g- and A-matrices of theCu(II) ion and the anisotropic ZFS parameters of the homodimer. Within the experimental error, the Cu(II) g-matrix obtained for the diluted compound was identical to that previously determinedby us in pure Cu(tda)(phen). The ZFS is shown to be dominated by magnetic dipolar coupling between the unpaired electrons mainly centered around theCu(II) ions, although partially delocalized over the equatorial copper ligands. DFT calculations yielded spin population values compatible with those determined from the analysis of the anisotropic ZFS assuming a distributed dipole model. The information obtained from the diluted compound was used to evaluate the interdimeric exchange interaction between dimeric units in pure Cu(tda)(phen). The comparison between both point and distributed dipole approximations is discussed with reference to the analysis of the EPR data.
Fil: Neuman, Nicolás Ignacio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Burna, Emerson Roberto. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; Argentina
Fil: Passeggi, Mario Cesar Guillermo. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Rizzi, Alberto Claudio. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
Fil: Brondino, Carlos Dante. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe; Argentina. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas. Departamento de Física; Argentina
description We report the synthesis and X-ray structure of the dimeric zinc(II) compound [Zn(tda)(phen)]2∙H2tda,(tda = thiodiacetic acid, phen = 1,10-phenanthroline) hereafter Zn(tda)(phen),and a single crystal EPR study of Zn(tda)(phen) doped with Cu(II) ions. Zn(tda)(phen)is isomorphous to its Cu(II) analogue. The EPR spectra show a central signal composed of one to four resonances assigned to Cu-Zn heterodimers, flanked by less intense satellite signals assigned to Cu-Cu homodimers. Analysis of single crystal EPR data allowed us to determine the g- and A-matrices of theCu(II) ion and the anisotropic ZFS parameters of the homodimer. Within the experimental error, the Cu(II) g-matrix obtained for the diluted compound was identical to that previously determinedby us in pure Cu(tda)(phen). The ZFS is shown to be dominated by magnetic dipolar coupling between the unpaired electrons mainly centered around theCu(II) ions, although partially delocalized over the equatorial copper ligands. DFT calculations yielded spin population values compatible with those determined from the analysis of the anisotropic ZFS assuming a distributed dipole model. The information obtained from the diluted compound was used to evaluate the interdimeric exchange interaction between dimeric units in pure Cu(tda)(phen). The comparison between both point and distributed dipole approximations is discussed with reference to the analysis of the EPR data.
publishDate 2015
dc.date.none.fl_str_mv 2015-01
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/11336/247818
Neuman, Nicolás Ignacio; Burna, Emerson Roberto; Baggio, Ricardo Fortunato; Passeggi, Mario Cesar Guillermo; Rizzi, Alberto Claudio; et al.; Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy; Royal Society of Chemistry; Inorganic Chemistry Frontiers; 2; 9; 1-2015; 837-845
2052-1553
CONICET Digital
CONICET
url http://hdl.handle.net/11336/247818
identifier_str_mv Neuman, Nicolás Ignacio; Burna, Emerson Roberto; Baggio, Ricardo Fortunato; Passeggi, Mario Cesar Guillermo; Rizzi, Alberto Claudio; et al.; Transition from isolated to interacting copper( ii ) pairs in extended lattices evaluated by single crystal EPR spectroscopy; Royal Society of Chemistry; Inorganic Chemistry Frontiers; 2; 9; 1-2015; 837-845
2052-1553
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2015/qi/c5qi00086f
info:eu-repo/semantics/altIdentifier/doi/10.1039/C5QI00086F
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 Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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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