Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties

Autores
Funes, Víctor Alejandro; Carrella, Luca; Sorace, Lorenzo; Rentschler, Eva; Alborés, Pablo
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We are reporting two new mixed valent Co(ii)/Co(iii) polynuclear complexes, {Co II 6 Co III 3 } and {Co II Co III 4 }, bearing different amount of Co(ii) ions in their cores, through the employment of the multidentate triethanolamine (teaH 3 ) ligand in different stoichiometric ratios. We present a complete picture of the magnetic behaviour of both complexes through a combined usage of the susceptibility, magnetization and X-band EPR data as well as broken-symmetry DFT calculations. Compound 1 shows an atypical spin-only behaviour, probably due to the presence of four and five coordinated Co(ii) sites as well as highly distorted six coordinated Co(ii) ions, promoting a high degree of orbital contribution quenching. Through the usage of a simplified exchange coupling scheme and relying on DFT based magneto-structural correlation we have been able to explain the observed diamagnetic ground state. Concerning compound 2, DC magnetic data supported by X-band EPR measurements suggest the existence of anisotropy with a zero-field splitting parameter D, at least in the range of 2-10 cm -1 . In agreement with this description, a slow relaxation of magnetization is observed after applying a small external magnetic field, under AC measurements. Field and temperature dependence of the characteristic relaxation time establishes a thermal barrier for magnetization reversal of about 25 cm -1 , which is in good agreement with the energy splitting of the |±1/2〉 and |±3/2〉 doublets established from static magnetic measurements.
Fil: Funes, Víctor Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Carrella, Luca. Johannes Gutenberg Universitat Mainz; Alemania
Fil: Sorace, Lorenzo. Università di Firenze; Italia
Fil: Rentschler, Eva. Johannes Gutenberg Universitat Mainz; Alemania
Fil: Alborés, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Materia
Cobalt
Magnetic Properties
Mixed-Valent Compounds
Cluster Compounds
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:11336/83702
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/83702
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic propertiesFunes, Víctor AlejandroCarrella, LucaSorace, LorenzoRentschler, EvaAlborés, PabloCobaltMagnetic PropertiesMixed-Valent CompoundsCluster Compoundshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We are reporting two new mixed valent Co(ii)/Co(iii) polynuclear complexes, {Co II 6 Co III 3 } and {Co II Co III 4 }, bearing different amount of Co(ii) ions in their cores, through the employment of the multidentate triethanolamine (teaH 3 ) ligand in different stoichiometric ratios. We present a complete picture of the magnetic behaviour of both complexes through a combined usage of the susceptibility, magnetization and X-band EPR data as well as broken-symmetry DFT calculations. Compound 1 shows an atypical spin-only behaviour, probably due to the presence of four and five coordinated Co(ii) sites as well as highly distorted six coordinated Co(ii) ions, promoting a high degree of orbital contribution quenching. Through the usage of a simplified exchange coupling scheme and relying on DFT based magneto-structural correlation we have been able to explain the observed diamagnetic ground state. Concerning compound 2, DC magnetic data supported by X-band EPR measurements suggest the existence of anisotropy with a zero-field splitting parameter D, at least in the range of 2-10 cm -1 . In agreement with this description, a slow relaxation of magnetization is observed after applying a small external magnetic field, under AC measurements. Field and temperature dependence of the characteristic relaxation time establishes a thermal barrier for magnetization reversal of about 25 cm -1 , which is in good agreement with the energy splitting of the |±1/2〉 and |±3/2〉 doublets established from static magnetic measurements.Fil: Funes, Víctor Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaFil: Carrella, Luca. Johannes Gutenberg Universitat Mainz; AlemaniaFil: Sorace, Lorenzo. Università di Firenze; ItaliaFil: Rentschler, Eva. Johannes Gutenberg Universitat Mainz; AlemaniaFil: Alborés, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; ArgentinaRoyal Society of Chemistry2015-02info: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/11336/83702Funes, Víctor Alejandro; Carrella, Luca; Sorace, Lorenzo; Rentschler, Eva; Alborés, Pablo; Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties; Royal Society of Chemistry; Dalton Transactions; 44; 5; 2-2015; 2390-24001477-9226CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/C4DT03034Finfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2015/DT/C4DT03034Finfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:00:18Zoai:ri.conicet.gov.ar:11336/83702instacron: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:34982025-10-22 11:00:18.432CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties
title Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties
spellingShingle Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties
Funes, Víctor Alejandro
Cobalt
Magnetic Properties
Mixed-Valent Compounds
Cluster Compounds
title_short Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties
title_full Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties
title_fullStr Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties
title_full_unstemmed Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties
title_sort Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties
dc.creator.none.fl_str_mv Funes, Víctor Alejandro
Carrella, Luca
Sorace, Lorenzo
Rentschler, Eva
Alborés, Pablo
author Funes, Víctor Alejandro
author_facet Funes, Víctor Alejandro
Carrella, Luca
Sorace, Lorenzo
Rentschler, Eva
Alborés, Pablo
author_role author
author2 Carrella, Luca
Sorace, Lorenzo
Rentschler, Eva
Alborés, Pablo
author2_role author
author
author
author
dc.subject.none.fl_str_mv Cobalt
Magnetic Properties
Mixed-Valent Compounds
Cluster Compounds
topic Cobalt
Magnetic Properties
Mixed-Valent Compounds
Cluster Compounds
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 are reporting two new mixed valent Co(ii)/Co(iii) polynuclear complexes, {Co II 6 Co III 3 } and {Co II Co III 4 }, bearing different amount of Co(ii) ions in their cores, through the employment of the multidentate triethanolamine (teaH 3 ) ligand in different stoichiometric ratios. We present a complete picture of the magnetic behaviour of both complexes through a combined usage of the susceptibility, magnetization and X-band EPR data as well as broken-symmetry DFT calculations. Compound 1 shows an atypical spin-only behaviour, probably due to the presence of four and five coordinated Co(ii) sites as well as highly distorted six coordinated Co(ii) ions, promoting a high degree of orbital contribution quenching. Through the usage of a simplified exchange coupling scheme and relying on DFT based magneto-structural correlation we have been able to explain the observed diamagnetic ground state. Concerning compound 2, DC magnetic data supported by X-band EPR measurements suggest the existence of anisotropy with a zero-field splitting parameter D, at least in the range of 2-10 cm -1 . In agreement with this description, a slow relaxation of magnetization is observed after applying a small external magnetic field, under AC measurements. Field and temperature dependence of the characteristic relaxation time establishes a thermal barrier for magnetization reversal of about 25 cm -1 , which is in good agreement with the energy splitting of the |±1/2〉 and |±3/2〉 doublets established from static magnetic measurements.
Fil: Funes, Víctor Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
Fil: Carrella, Luca. Johannes Gutenberg Universitat Mainz; Alemania
Fil: Sorace, Lorenzo. Università di Firenze; Italia
Fil: Rentschler, Eva. Johannes Gutenberg Universitat Mainz; Alemania
Fil: Alborés, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina
description We are reporting two new mixed valent Co(ii)/Co(iii) polynuclear complexes, {Co II 6 Co III 3 } and {Co II Co III 4 }, bearing different amount of Co(ii) ions in their cores, through the employment of the multidentate triethanolamine (teaH 3 ) ligand in different stoichiometric ratios. We present a complete picture of the magnetic behaviour of both complexes through a combined usage of the susceptibility, magnetization and X-band EPR data as well as broken-symmetry DFT calculations. Compound 1 shows an atypical spin-only behaviour, probably due to the presence of four and five coordinated Co(ii) sites as well as highly distorted six coordinated Co(ii) ions, promoting a high degree of orbital contribution quenching. Through the usage of a simplified exchange coupling scheme and relying on DFT based magneto-structural correlation we have been able to explain the observed diamagnetic ground state. Concerning compound 2, DC magnetic data supported by X-band EPR measurements suggest the existence of anisotropy with a zero-field splitting parameter D, at least in the range of 2-10 cm -1 . In agreement with this description, a slow relaxation of magnetization is observed after applying a small external magnetic field, under AC measurements. Field and temperature dependence of the characteristic relaxation time establishes a thermal barrier for magnetization reversal of about 25 cm -1 , which is in good agreement with the energy splitting of the |±1/2〉 and |±3/2〉 doublets established from static magnetic measurements.
publishDate 2015
dc.date.none.fl_str_mv 2015-02
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/11336/83702
Funes, Víctor Alejandro; Carrella, Luca; Sorace, Lorenzo; Rentschler, Eva; Alborés, Pablo; Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties; Royal Society of Chemistry; Dalton Transactions; 44; 5; 2-2015; 2390-2400
1477-9226
CONICET Digital
CONICET
url http://hdl.handle.net/11336/83702
identifier_str_mv Funes, Víctor Alejandro; Carrella, Luca; Sorace, Lorenzo; Rentschler, Eva; Alborés, Pablo; Switching nuclearity and Co(II) content through stoichiometry adjustment: {Co II 6 Co III 3 } and {Co II Co 4 III } mixed valent complexes and a study of their magnetic properties; Royal Society of Chemistry; Dalton Transactions; 44; 5; 2-2015; 2390-2400
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/doi/10.1039/C4DT03034F
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2015/DT/C4DT03034F
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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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 12.982451

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