Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR

Autores
Sartoris, Rosana Patricia; Nascimento, Otaciro R.; Santana, Ricardo C.; Perec, Mireille; Baggio, Ricardo Fortunato; Calvo, Rafael
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A binuclear CuII compound [Cu2(bpa)2(P2O7)(H2O)2]·2.5H2O, 1, (bpa = 2,2-bipyridylamine), with pairs of CuII ions bridged by one pyrophosphate tetra-anion, was synthesized and crystallized. Its triclinic structure was determined by single-crystal X-ray diffraction. Electron paramagnetic resonance (EPR) spectra of single crystal samples of 1 were recorded for a fixed orientation of the magnetic field (B0) as a function oftemperature (T) between 4.7 and 293 K, and at T = 4.7, 50 and 293 K, as a function of the orientation of B0. Below ∼8 K, the spectra are assigned to two types of mononuclear crystal defects hyperfine-coupled to one copper and two nitrogen nuclei. The g-matrices and hyperfine couplings at these T provide information about the structures of these defects. Above 10 K, the spectrum is dominated by the response of the bulk binuclear CuII material, showing hyperfine interactions with two copper nuclei, collapsing to asingle peak above 18 K when the units are magnetically connected, and the magnetic behaviour becomes 3D. We attribute the results above 10 K to the interplay of an AFM intrabinuclear exchange interaction J0 = −28(3) cm−1 (defined as Hex = −J0S1·S2), and three orders of magnitude weaker exchange coupling with average magnitude |J1| ≥ 0.022 cm−1 between CuII ions in neighbouring binuclear units. The interplays between structure, exchange couplings, magnetic dimension and spin dynamics in the binuclear compoundare discussed. A previously unreported situation, where the structure of the spectra arising from the anisotropic spin?spin interaction term (D) within the binuclear unit is averaged out, but the forbidden half field transition is not, is observed and explained.
Fil: Sartoris, Rosana Patricia. Universidad Nacional del Litoral; Argentina
Fil: Nascimento, Otaciro R.. Universidade de Sao Paulo; Brasil
Fil: Santana, Ricardo C.. Universidade Federal de Goiás; Brasil
Fil: Perec, Mireille. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; Argentina
Fil: Calvo, Rafael. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina
Materia
COBRE DINUCLEAR
DIMENSIÓN MAGNÉTICA
INTERCAMBIO
RPE
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:11336/113458
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPRSartoris, Rosana PatriciaNascimento, Otaciro R.Santana, Ricardo C.Perec, MireilleBaggio, Ricardo FortunatoCalvo, RafaelCOBRE DINUCLEARDIMENSIÓN MAGNÉTICAINTERCAMBIORPEhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1A binuclear CuII compound [Cu2(bpa)2(P2O7)(H2O)2]·2.5H2O, 1, (bpa = 2,2-bipyridylamine), with pairs of CuII ions bridged by one pyrophosphate tetra-anion, was synthesized and crystallized. Its triclinic structure was determined by single-crystal X-ray diffraction. Electron paramagnetic resonance (EPR) spectra of single crystal samples of 1 were recorded for a fixed orientation of the magnetic field (B0) as a function oftemperature (T) between 4.7 and 293 K, and at T = 4.7, 50 and 293 K, as a function of the orientation of B0. Below ∼8 K, the spectra are assigned to two types of mononuclear crystal defects hyperfine-coupled to one copper and two nitrogen nuclei. The g-matrices and hyperfine couplings at these T provide information about the structures of these defects. Above 10 K, the spectrum is dominated by the response of the bulk binuclear CuII material, showing hyperfine interactions with two copper nuclei, collapsing to asingle peak above 18 K when the units are magnetically connected, and the magnetic behaviour becomes 3D. We attribute the results above 10 K to the interplay of an AFM intrabinuclear exchange interaction J0 = −28(3) cm−1 (defined as Hex = −J0S1·S2), and three orders of magnitude weaker exchange coupling with average magnitude |J1| ≥ 0.022 cm−1 between CuII ions in neighbouring binuclear units. The interplays between structure, exchange couplings, magnetic dimension and spin dynamics in the binuclear compoundare discussed. A previously unreported situation, where the structure of the spectra arising from the anisotropic spin?spin interaction term (D) within the binuclear unit is averaged out, but the forbidden half field transition is not, is observed and explained.Fil: Sartoris, Rosana Patricia. Universidad Nacional del Litoral; ArgentinaFil: Nascimento, Otaciro R.. Universidade de Sao Paulo; BrasilFil: Santana, Ricardo C.. Universidade Federal de Goiás; BrasilFil: Perec, Mireille. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; ArgentinaFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; ArgentinaFil: Calvo, Rafael. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; 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/pdfhttp://hdl.handle.net/11336/113458Sartoris, Rosana Patricia; Nascimento, Otaciro R.; Santana, Ricardo C.; Perec, Mireille; Baggio, Ricardo Fortunato; et al.; Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR; Royal Society of Chemistry; Dalton Transactions; 44; 1-2015; 4732-47431477-9226CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlepdf/2015/DT/C4DT03616Finfo:eu-repo/semantics/altIdentifier/doi/10.1039/c3dt32799jinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:58:15Zoai:ri.conicet.gov.ar:11336/113458instacron: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:34982025-09-03 09:58:16.043CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR
title Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR
spellingShingle Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR
Sartoris, Rosana Patricia
COBRE DINUCLEAR
DIMENSIÓN MAGNÉTICA
INTERCAMBIO
RPE
title_short Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR
title_full Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR
title_fullStr Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR
title_full_unstemmed Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR
title_sort Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR
dc.creator.none.fl_str_mv Sartoris, Rosana Patricia
Nascimento, Otaciro R.
Santana, Ricardo C.
Perec, Mireille
Baggio, Ricardo Fortunato
Calvo, Rafael
author Sartoris, Rosana Patricia
author_facet Sartoris, Rosana Patricia
Nascimento, Otaciro R.
Santana, Ricardo C.
Perec, Mireille
Baggio, Ricardo Fortunato
Calvo, Rafael
author_role author
author2 Nascimento, Otaciro R.
Santana, Ricardo C.
Perec, Mireille
Baggio, Ricardo Fortunato
Calvo, Rafael
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv COBRE DINUCLEAR
DIMENSIÓN MAGNÉTICA
INTERCAMBIO
RPE
topic COBRE DINUCLEAR
DIMENSIÓN MAGNÉTICA
INTERCAMBIO
RPE
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv A binuclear CuII compound [Cu2(bpa)2(P2O7)(H2O)2]·2.5H2O, 1, (bpa = 2,2-bipyridylamine), with pairs of CuII ions bridged by one pyrophosphate tetra-anion, was synthesized and crystallized. Its triclinic structure was determined by single-crystal X-ray diffraction. Electron paramagnetic resonance (EPR) spectra of single crystal samples of 1 were recorded for a fixed orientation of the magnetic field (B0) as a function oftemperature (T) between 4.7 and 293 K, and at T = 4.7, 50 and 293 K, as a function of the orientation of B0. Below ∼8 K, the spectra are assigned to two types of mononuclear crystal defects hyperfine-coupled to one copper and two nitrogen nuclei. The g-matrices and hyperfine couplings at these T provide information about the structures of these defects. Above 10 K, the spectrum is dominated by the response of the bulk binuclear CuII material, showing hyperfine interactions with two copper nuclei, collapsing to asingle peak above 18 K when the units are magnetically connected, and the magnetic behaviour becomes 3D. We attribute the results above 10 K to the interplay of an AFM intrabinuclear exchange interaction J0 = −28(3) cm−1 (defined as Hex = −J0S1·S2), and three orders of magnitude weaker exchange coupling with average magnitude |J1| ≥ 0.022 cm−1 between CuII ions in neighbouring binuclear units. The interplays between structure, exchange couplings, magnetic dimension and spin dynamics in the binuclear compoundare discussed. A previously unreported situation, where the structure of the spectra arising from the anisotropic spin?spin interaction term (D) within the binuclear unit is averaged out, but the forbidden half field transition is not, is observed and explained.
Fil: Sartoris, Rosana Patricia. Universidad Nacional del Litoral; Argentina
Fil: Nascimento, Otaciro R.. Universidade de Sao Paulo; Brasil
Fil: Santana, Ricardo C.. Universidade Federal de Goiás; Brasil
Fil: Perec, Mireille. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica; Argentina
Fil: Calvo, Rafael. Universidad Nacional del Litoral. Facultad de Bioquímica y Ciencias Biológicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Física del Litoral. Universidad Nacional del Litoral. Instituto de Física del Litoral; Argentina
description A binuclear CuII compound [Cu2(bpa)2(P2O7)(H2O)2]·2.5H2O, 1, (bpa = 2,2-bipyridylamine), with pairs of CuII ions bridged by one pyrophosphate tetra-anion, was synthesized and crystallized. Its triclinic structure was determined by single-crystal X-ray diffraction. Electron paramagnetic resonance (EPR) spectra of single crystal samples of 1 were recorded for a fixed orientation of the magnetic field (B0) as a function oftemperature (T) between 4.7 and 293 K, and at T = 4.7, 50 and 293 K, as a function of the orientation of B0. Below ∼8 K, the spectra are assigned to two types of mononuclear crystal defects hyperfine-coupled to one copper and two nitrogen nuclei. The g-matrices and hyperfine couplings at these T provide information about the structures of these defects. Above 10 K, the spectrum is dominated by the response of the bulk binuclear CuII material, showing hyperfine interactions with two copper nuclei, collapsing to asingle peak above 18 K when the units are magnetically connected, and the magnetic behaviour becomes 3D. We attribute the results above 10 K to the interplay of an AFM intrabinuclear exchange interaction J0 = −28(3) cm−1 (defined as Hex = −J0S1·S2), and three orders of magnitude weaker exchange coupling with average magnitude |J1| ≥ 0.022 cm−1 between CuII ions in neighbouring binuclear units. The interplays between structure, exchange couplings, magnetic dimension and spin dynamics in the binuclear compoundare discussed. A previously unreported situation, where the structure of the spectra arising from the anisotropic spin?spin interaction term (D) within the binuclear unit is averaged out, but the forbidden half field transition is not, is observed and explained.
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/11336/113458
Sartoris, Rosana Patricia; Nascimento, Otaciro R.; Santana, Ricardo C.; Perec, Mireille; Baggio, Ricardo Fortunato; et al.; Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR; Royal Society of Chemistry; Dalton Transactions; 44; 1-2015; 4732-4743
1477-9226
CONICET Digital
CONICET
url http://hdl.handle.net/11336/113458
identifier_str_mv Sartoris, Rosana Patricia; Nascimento, Otaciro R.; Santana, Ricardo C.; Perec, Mireille; Baggio, Ricardo Fortunato; et al.; Structure and magnetism of a binuclear CuII pyrophosphate: transition to a 3D magnetic behaviour studied by single crystal EPR; Royal Society of Chemistry; Dalton Transactions; 44; 1-2015; 4732-4743
1477-9226
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.rsc.org/en/content/articlepdf/2015/DT/C4DT03616F
info:eu-repo/semantics/altIdentifier/doi/10.1039/c3dt32799j
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
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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score 13.13397

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