Mixed-valent linear CoIII2CoII complexes having an easy-axis magnetic anisotropy: Experimental and theoretical investigation.

Abstract

An in situ generated ligand formed by the Schiff base condensation of 3,5-di-tert-butylsalicylaldehyde and R(-) or S(+) 2-phenylglycinol was reacted with cobalt(II) acetate tetrahydrate affording a mixed-valent enantiomerically pure [CoIICoIII2(R or S-L1)2 (L2)2(CO2CH3)2] complexes 1-R and 1-S {where L1 = (R) or (S)-2,4-di-tert-butyl-6-(4-hydroxo-3-phenylbut-1-en-1-yl)phenolate and L2 = (R) or (S) 2-phenylglycinolate} complexes having linear trinuclear metal cores. The X-ray structure and BVS analysis revealed the linear arrangement of metal cores with the central cobalt ion in a +2 oxidation state, while the terminal cobalt ions are in a +3 oxidation state. The fitting of the DC magnetic data revealed an easy-axis magnetic anisotropy with D = -58.6 cm-1 (E/D = 0.257) for the Co (II) ion in 1-R. The ac magnetic susceptibility measurements confirm the field-induced dynamic magnetic behavior of 1-R with the relaxation of the magnetization, which occurs through a combination of Raman and direct processes. Further CASSCF-based ab initio and NEVPT2 theoretical investigations on the X-ray structure of 1-R (or 1-S) provide D values of -60.0 cm-1 (E/D = 0.276) and -57.4 cm-1 (E/D = 0.296), respectively, and help in rationalizing our experimental findings.

Supplementary files

Article information

Article type
Paper
Submitted
06 May 2025
Accepted
18 Jul 2025
First published
18 Jul 2025

Dalton Trans., 2025, Accepted Manuscript

Mixed-valent linear CoIII2CoII complexes having an easy-axis magnetic anisotropy: Experimental and theoretical investigation.

V. Chandrasekhar, P. Kalita, R. Nabi, T. Guizouarn, F. Pointillart, X.-G. Zhang and N. Ahmed, Dalton Trans., 2025, Accepted Manuscript , DOI: 10.1039/D5DT01060H

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