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dc.contributor.author
Neuman, Nicolás Ignacio
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Winkler, Elin Lilian
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Peña, Octavio
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Passeggi, Mario Cesar Guillermo
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Rizzi, Alberto Claudio
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Brondino, Carlos Dante
dc.date.available
2017-11-03T17:26:44Z
dc.date.issued
2014-02
dc.identifier.citation
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
dc.identifier.issn
0020-1669
dc.identifier.uri
http://hdl.handle.net/11336/27560
dc.description.abstract
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.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.subject
Cobalt
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Exchange Interaction
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Single Crystal Epr
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Zero Field Splitting
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Otras Ciencias Químicas
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Ciencias Químicas
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CIENCIAS NATURALES Y EXACTAS
dc.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
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2017-09-29T16:43:45Z
dc.journal.volume
53
dc.journal.number
5
dc.journal.pagination
2535-2544
dc.journal.pais
Estados Unidos
dc.description.fil
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
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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
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Fil: Peña, Octavio. Universite de Rennes I. Institut Des Sciences Chimiques de Rennes.; Francia
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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
dc.description.fil
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
dc.description.fil
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
dc.journal.title
Inorganic Chemistry
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1021/ic402797t
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/ic402797t
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