Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements...

Autores: Neuman, Nicolás Ignacio; Winkler, Elin Lilian; Peña, Octavio; Passeggi, Mario Cesar Guillermo; Rizzi, Alberto Claudio; Brondino, Carlos Dante
Año de publicación: 2014
Idioma: inglés
Tipo de recurso: artículo
Estado: versión publicada
Descripción: We report single-crystal X-band EPR and magnetic measurements of the coordination polymer catena-(trans-(μ2-fumarato)tetraaquacobalt(II)), 1, and the Co(II)-doped Zn(II) analogue, 2, in different Zn:Co ratios. 1 presents two magnetically inequivalent high spin S = 3/2 Co(II) ions per unit cell, named A and B, in a distorted octahedral environment coordinated to four water oxygen atoms and trans coordinated to two carboxylic oxygen atoms from the fumarate anions, in which the Co(II) ions are linked by hydrogen bonds and fumarate molecules. Magnetic susceptibility and magnetization measurements of 1 indicate weak antiferromagnetic exchange interactions between the S = 3/2 spins of the Co(II) ions in the crystal lattice. Oriented single crystal EPR experiments of 1 and 2 were used to evaluate the molecular g-tensor and the different exchange coupling constants between the Co(II) ions, assuming an effective spin S′= 1/2. Unexpectedly, the eigenvectors of the molecular g-tensor were not lying along any preferential bond direction, indicating that, in high spin Co(II) ions in roughly octahedral geometry with approximately axial EPR signals, the presence of molecular pseudo axes in the metal site does not determine preferential directions for the molecular g-tensor. The EPR experiment and magnetic measurements, together with a theoretical analysis relating the coupling constants obtained from both techniques, allowed us to evaluate selectively the exchange coupling constant associated with hydrogen bonds that connect magnetically inequivalent Co(II) ions (|JAB1/2| = 0.055(2) cm?1) and the exchange coupling constant associated with a fumarate bridge connecting equivalent Co(II) ions (|JAA1/2| ≈ 0.25 (1) cm?1), in good agreement with the average J3/2 value determined from magnetic measurements.
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: Winkler, Elin Lilian. Comision Nacional de Energia Atomica. Fundación Jose A. Balseiro; Argentina. Universidad Nacional de Cuyo; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Peña, Octavio. Universite de Rennes I. Institut Des Sciences Chimiques de Rennes.; Francia
Fil: Passeggi, Mario Cesar Guillermo. 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: Rizzi, Alberto Claudio. 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: Brondino, Carlos Dante. 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
Materia: Cobalt
Exchange Interaction
Single Crystal Epr
Zero Field Splitting
Nivel de accesibilidad: acceso abierto
Condiciones de uso: https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
Institución: Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador: oai:ri.conicet.gov.ar:11336/27560

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spelling	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic MeasurementsNeuman, Nicolás IgnacioWinkler, Elin LilianPeña, OctavioPasseggi, Mario Cesar GuillermoRizzi, Alberto ClaudioBrondino, Carlos DanteCobaltExchange InteractionSingle Crystal EprZero Field Splittinghttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report single-crystal X-band EPR and magnetic measurements of the coordination polymer catena-(trans-(μ2-fumarato)tetraaquacobalt(II)), 1, and the Co(II)-doped Zn(II) analogue, 2, in different Zn:Co ratios. 1 presents two magnetically inequivalent high spin S = 3/2 Co(II) ions per unit cell, named A and B, in a distorted octahedral environment coordinated to four water oxygen atoms and trans coordinated to two carboxylic oxygen atoms from the fumarate anions, in which the Co(II) ions are linked by hydrogen bonds and fumarate molecules. Magnetic susceptibility and magnetization measurements of 1 indicate weak antiferromagnetic exchange interactions between the S = 3/2 spins of the Co(II) ions in the crystal lattice. Oriented single crystal EPR experiments of 1 and 2 were used to evaluate the molecular g-tensor and the different exchange coupling constants between the Co(II) ions, assuming an effective spin S′= 1/2. Unexpectedly, the eigenvectors of the molecular g-tensor were not lying along any preferential bond direction, indicating that, in high spin Co(II) ions in roughly octahedral geometry with approximately axial EPR signals, the presence of molecular pseudo axes in the metal site does not determine preferential directions for the molecular g-tensor. The EPR experiment and magnetic measurements, together with a theoretical analysis relating the coupling constants obtained from both techniques, allowed us to evaluate selectively the exchange coupling constant associated with hydrogen bonds that connect magnetically inequivalent Co(II) ions (\|JAB1/2\| = 0.055(2) cm?1) and the exchange coupling constant associated with a fumarate bridge connecting equivalent Co(II) ions (\|JAA1/2\| ≈ 0.25 (1) cm?1), in good agreement with the average J3/2 value determined from magnetic measurements.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: Winkler, Elin Lilian. Comision Nacional de Energia Atomica. Fundación Jose A. Balseiro; Argentina. Universidad Nacional de Cuyo; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Peña, Octavio. Universite de Rennes I. Institut Des Sciences Chimiques de Rennes.; FranciaFil: Passeggi, Mario Cesar Guillermo. 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: Rizzi, Alberto Claudio. 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: Brondino, Carlos Dante. 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; ArgentinaAmerican Chemical Society2014-02info: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/11336/27560Neuman, Nicolás Ignacio; Winkler, Elin Lilian; Peña, Octavio; Passeggi, Mario Cesar Guillermo; Rizzi, Alberto Claudio; et al.; Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements; American Chemical Society; Inorganic Chemistry; 53; 5; 2-2014; 2535-25440020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic402797tinfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ic402797tinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:00:59Zoai:ri.conicet.gov.ar:11336/27560instacron: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 10:00:59.591CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements
title	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements
spellingShingle	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements Neuman, Nicolás Ignacio Cobalt Exchange Interaction Single Crystal Epr Zero Field Splitting
title_short	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements
title_full	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements
title_fullStr	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements
title_full_unstemmed	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements
title_sort	Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements
dc.creator.none.fl_str_mv	Neuman, Nicolás Ignacio Winkler, Elin Lilian Peña, Octavio Passeggi, Mario Cesar Guillermo Rizzi, Alberto Claudio Brondino, Carlos Dante
author	Neuman, Nicolás Ignacio
author_facet	Neuman, Nicolás Ignacio Winkler, Elin Lilian Peña, Octavio Passeggi, Mario Cesar Guillermo Rizzi, Alberto Claudio Brondino, Carlos Dante
author_role	author
author2	Winkler, Elin Lilian Peña, Octavio Passeggi, Mario Cesar Guillermo Rizzi, Alberto Claudio Brondino, Carlos Dante
author2_role	author author author author author
dc.subject.none.fl_str_mv	Cobalt Exchange Interaction Single Crystal Epr Zero Field Splitting
topic	Cobalt Exchange Interaction Single Crystal Epr Zero Field Splitting
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 single-crystal X-band EPR and magnetic measurements of the coordination polymer catena-(trans-(μ2-fumarato)tetraaquacobalt(II)), 1, and the Co(II)-doped Zn(II) analogue, 2, in different Zn:Co ratios. 1 presents two magnetically inequivalent high spin S = 3/2 Co(II) ions per unit cell, named A and B, in a distorted octahedral environment coordinated to four water oxygen atoms and trans coordinated to two carboxylic oxygen atoms from the fumarate anions, in which the Co(II) ions are linked by hydrogen bonds and fumarate molecules. Magnetic susceptibility and magnetization measurements of 1 indicate weak antiferromagnetic exchange interactions between the S = 3/2 spins of the Co(II) ions in the crystal lattice. Oriented single crystal EPR experiments of 1 and 2 were used to evaluate the molecular g-tensor and the different exchange coupling constants between the Co(II) ions, assuming an effective spin S′= 1/2. Unexpectedly, the eigenvectors of the molecular g-tensor were not lying along any preferential bond direction, indicating that, in high spin Co(II) ions in roughly octahedral geometry with approximately axial EPR signals, the presence of molecular pseudo axes in the metal site does not determine preferential directions for the molecular g-tensor. The EPR experiment and magnetic measurements, together with a theoretical analysis relating the coupling constants obtained from both techniques, allowed us to evaluate selectively the exchange coupling constant associated with hydrogen bonds that connect magnetically inequivalent Co(II) ions (\|JAB1/2\| = 0.055(2) cm?1) and the exchange coupling constant associated with a fumarate bridge connecting equivalent Co(II) ions (\|JAA1/2\| ≈ 0.25 (1) cm?1), in good agreement with the average J3/2 value determined from magnetic measurements. 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: Winkler, Elin Lilian. Comision Nacional de Energia Atomica. Fundación Jose A. Balseiro; Argentina. Universidad Nacional de Cuyo; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Peña, Octavio. Universite de Rennes I. Institut Des Sciences Chimiques de Rennes.; Francia Fil: Passeggi, Mario Cesar Guillermo. 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: Rizzi, Alberto Claudio. 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: Brondino, Carlos Dante. 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
description	We report single-crystal X-band EPR and magnetic measurements of the coordination polymer catena-(trans-(μ2-fumarato)tetraaquacobalt(II)), 1, and the Co(II)-doped Zn(II) analogue, 2, in different Zn:Co ratios. 1 presents two magnetically inequivalent high spin S = 3/2 Co(II) ions per unit cell, named A and B, in a distorted octahedral environment coordinated to four water oxygen atoms and trans coordinated to two carboxylic oxygen atoms from the fumarate anions, in which the Co(II) ions are linked by hydrogen bonds and fumarate molecules. Magnetic susceptibility and magnetization measurements of 1 indicate weak antiferromagnetic exchange interactions between the S = 3/2 spins of the Co(II) ions in the crystal lattice. Oriented single crystal EPR experiments of 1 and 2 were used to evaluate the molecular g-tensor and the different exchange coupling constants between the Co(II) ions, assuming an effective spin S′= 1/2. Unexpectedly, the eigenvectors of the molecular g-tensor were not lying along any preferential bond direction, indicating that, in high spin Co(II) ions in roughly octahedral geometry with approximately axial EPR signals, the presence of molecular pseudo axes in the metal site does not determine preferential directions for the molecular g-tensor. The EPR experiment and magnetic measurements, together with a theoretical analysis relating the coupling constants obtained from both techniques, allowed us to evaluate selectively the exchange coupling constant associated with hydrogen bonds that connect magnetically inequivalent Co(II) ions (\|JAB1/2\| = 0.055(2) cm?1) and the exchange coupling constant associated with a fumarate bridge connecting equivalent Co(II) ions (\|JAA1/2\| ≈ 0.25 (1) cm?1), in good agreement with the average J3/2 value determined from magnetic measurements.
publishDate	2014
dc.date.none.fl_str_mv	2014-02
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/11336/27560 Neuman, Nicolás Ignacio; Winkler, Elin Lilian; Peña, Octavio; Passeggi, Mario Cesar Guillermo; Rizzi, Alberto Claudio; et al.; Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements; American Chemical Society; Inorganic Chemistry; 53; 5; 2-2014; 2535-2544 0020-1669 CONICET Digital CONICET
url	http://hdl.handle.net/11336/27560
identifier_str_mv	Neuman, Nicolás Ignacio; Winkler, Elin Lilian; Peña, Octavio; Passeggi, Mario Cesar Guillermo; Rizzi, Alberto Claudio; et al.; Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements; American Chemical Society; Inorganic Chemistry; 53; 5; 2-2014; 2535-2544 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/doi/10.1021/ic402797t info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ic402797t
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/
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dc.publisher.none.fl_str_mv	American Chemical Society
publisher.none.fl_str_mv	American Chemical Society
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repository.mail.fl_str_mv	dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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Magnetic Properties of Weakly Exchange-Coupled High Spin Co(II) Ions in Pseudooctahedral Coordination Evaluated by Single Crystal X‑Band EPR Spectroscopy and Magnetic Measurements...

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