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Abstract:

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. © The Royal Society of Chemistry 2015.

Registro:

Documento: Artículo
Título: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
Autor:Funes, A.V.; Carrella, L.; Sorace, L.; Rentschler, E.; Alborés, P.
Filiación:Departamento de Quimica Inorganica, Analitica Y Quimica Fisica/INQUIMAE (CONICET), Universidad de Buenos Aires, Ciudad Universitaria, Buenos Aires, C1428EHA, Argentina
Institute of Inorganic and Analytical Chemistry, Johannes Gutenberg - University of Mainz, Duesbergweg 10-14, Mainz, D-55128, Germany
Dipartimento di Chimica U. Schiff, UdR INSTM, Università di Firenze, Via della Lastruccia 3, Sesto Fiorentino, Firenze, 50019, Italy
Palabras clave:Ground state; Magnetic relaxation measurement; Magnetism; Magnetization; Magnetization reversal; Temperature distribution; Characteristic relaxation time; External magnetic field; Magnetostructural correlations; Mixed-valent complexes; Orbital contribution; Polynuclear complexes; Temperature dependence; Zero-field splitting parameters; Cobalt compounds
Año:2015
Volumen:44
Número:5
Página de inicio:2390
Página de fin:2400
DOI: http://dx.doi.org/10.1039/c4dt03034f
Título revista:Dalton Transactions
Título revista abreviado:Dalton Trans.
ISSN:14779226
CODEN:DTARA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v44_n5_p2390_Funes

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Citas:

---------- APA ----------
Funes, A.V., Carrella, L., Sorace, L., Rentschler, E. & Alborés, P. (2015) . 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. Dalton Transactions, 44(5), 2390-2400.
http://dx.doi.org/10.1039/c4dt03034f
---------- CHICAGO ----------
Funes, A.V., Carrella, L., Sorace, L., Rentschler, E., Alborés, P. "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" . Dalton Transactions 44, no. 5 (2015) : 2390-2400.
http://dx.doi.org/10.1039/c4dt03034f
---------- MLA ----------
Funes, A.V., Carrella, L., Sorace, L., Rentschler, E., Alborés, P. "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" . Dalton Transactions, vol. 44, no. 5, 2015, pp. 2390-2400.
http://dx.doi.org/10.1039/c4dt03034f
---------- VANCOUVER ----------
Funes, A.V., Carrella, L., Sorace, L., Rentschler, E., Alborés, P. 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. Dalton Trans. 2015;44(5):2390-2400.
http://dx.doi.org/10.1039/c4dt03034f