Structural characterization and magnetic property studies of a mixed-valence {CoIIICo4II} complex with a μ4-oxo tetrahedral {Co4II} motif

Publication type:
Journal article
Metadata:
Autoren
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000509360800039&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1039/c9dt03561c
eISSN
1477-9234
Externe Identifier
  • Clarivate Analytics Document Solution ID: KF6PD
  • PubMed Identifier: 31868190
ISSN
1477-9226
Ausgabe der Veröffentlichung
3
Zeitschrift
DALTON TRANSACTIONS
Paginierung
932 - 940
Datum der Veröffentlichung
2020
Status
Published
Titel
Structural characterization and magnetic property studies of a mixed-valence {Co<SUP>III</SUP>Co<sub>4</sub><SUP>II</SUP>} complex with a μ<sub>4</sub>-oxo tetrahedral {Co<sub>4</sub><SUP>II</SUP>} motif
Sub types
  • Article
Ausgabe der Zeitschrift
49

Data source: Web of Science (Lite)

Other metadata sources:
Abstract
<p>We report a combined computational and experimental study of magnetic behaviour in a mixed valence {Co<sup>III</sup>Co<sup>II</sup>4} complex with a tetrahedral μ<sub>4</sub>O-CoII4 core.</p>
Autoren
DOI
10.1039/c9dt03561c
eISSN
1477-9234
ISSN
1477-9226
Ausgabe der Veröffentlichung
3
Zeitschrift
Dalton Transactions
Sprache
en
Online publication date
2020
Paginierung
932 - 940
Status
Published online
Herausgeber
Royal Society of Chemistry (RSC)
Herausgeber URL
http://dx.doi.org/10.1039/c9dt03561c
Datum der Datenerfassung
2024
Titel
Structural characterization and magnetic property studies of a mixed-valence {Co<sup>III</sup>CoII4} complex with a μ<sub>4</sub>-oxo tetrahedral {CoII4} motif
Ausgabe der Zeitschrift
49

Data source: Crossref

Abstract
We have synthesized and structurally characterized a new mixed valence pentanuclear Co complex, bearing a rare μ4-O-tetrahedral CoII4 unit, by employing a pyridine-like Schiff base ligand. We have performed DC magnetic susceptibility and magnetization measurements over polycrystalline samples and chemical quantum computations in order to understand the exchange interaction pattern within Co(ii) sites and ground state magnetic anisotropy. This new complex shows an overall antiferromagnetic exchange interaction whose strength strongly depends on the local symmetry of Co(ii) sites. Also, local ion magnetic anisotropy reveals a strongly axial behaviour with the lowest Kramers doublet (KD) at each Co(ii) ion sufficiently isolated from excited states at low temperatures. Two Co(ii) sites show tetrahedral symmetry and the spin only formalism including axial zero-field splitting (ZFS) term properly described them; on the other hand, the other two Co(ii) sites have distorted octahedral and square base pyramidal coordination spheres, and a strong orbital contribution leads to a failure of the spin only formalism. A model of four Seff = 1/2 exchange interacting sites is necessary in order to account for low temperature magnetization behaviour. In view of the strongly anisotropic KD states, the exchange interactions are forced to be modelled as anisotropic ones. Overall, experimental data and quantum chemical computations are in good agreement, supporting the proposed model for magnetic behaviour.
Addresses
  • Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE (CONICET), Facultad de Ciencias Exactas y Naturales Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina. albores@qi.fcen.uba.ar.
Autoren
DOI
10.1039/c9dt03561c
eISSN
1477-9234
Externe Identifier
  • PubMed Identifier: 31868190
Funding acknowledgements
  • Universidad de Buenos Aires:
  • Agencia Nacional de Promoción Científica y Tecnológica:
  • Consejo Nacional de Investigaciones Científicas y Técnicas:
Open access
false
ISSN
1477-9226
Ausgabe der Veröffentlichung
3
Zeitschrift
Dalton transactions (Cambridge, England : 2003)
Sprache
eng
Medium
Print
Paginierung
932 - 940
Datum der Veröffentlichung
2020
Status
Published
Datum der Datenerfassung
2019
Titel
Structural characterization and magnetic property studies of a mixed-valence {Co<sup>III</sup>Co} complex with a μ<sub>4</sub>-oxo tetrahedral {Co} motif.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
49

Data source: Europe PubMed Central

Abstract
We have synthesized and structurally characterized a new mixed valence pentanuclear Co complex, bearing a rare μ4-O-tetrahedral CoII4 unit, by employing a pyridine-like Schiff base ligand. We have performed DC magnetic susceptibility and magnetization measurements over polycrystalline samples and chemical quantum computations in order to understand the exchange interaction pattern within Co(ii) sites and ground state magnetic anisotropy. This new complex shows an overall antiferromagnetic exchange interaction whose strength strongly depends on the local symmetry of Co(ii) sites. Also, local ion magnetic anisotropy reveals a strongly axial behaviour with the lowest Kramers doublet (KD) at each Co(ii) ion sufficiently isolated from excited states at low temperatures. Two Co(ii) sites show tetrahedral symmetry and the spin only formalism including axial zero-field splitting (ZFS) term properly described them; on the other hand, the other two Co(ii) sites have distorted octahedral and square base pyramidal coordination spheres, and a strong orbital contribution leads to a failure of the spin only formalism. A model of four Seff = 1/2 exchange interacting sites is necessary in order to account for low temperature magnetization behaviour. In view of the strongly anisotropic KD states, the exchange interactions are forced to be modelled as anisotropic ones. Overall, experimental data and quantum chemical computations are in good agreement, supporting the proposed model for magnetic behaviour.
Autoren
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/31868190
DOI
10.1039/c9dt03561c
eISSN
1477-9234
Ausgabe der Veröffentlichung
3
Zeitschrift
Dalton Trans
Sprache
eng
Country
England
Paginierung
932 - 940
Datum der Veröffentlichung
2020
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2020
Titel
Structural characterization and magnetic property studies of a mixed-valence {CoIIICo} complex with a μ4-oxo tetrahedral {Co} motif.
Sub types
  • Journal Article
Ausgabe der Zeitschrift
49

Data source: PubMed

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