Field-induced single-ion magnets exhibiting tri-axial anisotropy in a 1D Co(II) coordination polymer with a rigid ligand 4,4'-(buta-1,3-diyne-1,4-diyl)dibenzoate.

Autor: Matos CRMO; Departamento de Química Inorgânica, Universidade Federal Fluminense (UFF), Outeiro de São João Batista, s/n, Campus do Valonguinho, Centro, 24020-141, Niterói, RJ, Brazil. cmronconi@id.uff.br., Sarmiento CV; Instituto de Física, Universidade Federal Fluminense (UFF), Niterói, RJ, 24210-346, Brazil., C Silva H Junior; Departamento de Química Inorgânica, Universidade Federal Fluminense (UFF), Outeiro de São João Batista, s/n, Campus do Valonguinho, Centro, 24020-141, Niterói, RJ, Brazil. cmronconi@id.uff.br., Ferreira GB; Departamento de Química Inorgânica, Universidade Federal Fluminense (UFF), Outeiro de São João Batista, s/n, Campus do Valonguinho, Centro, 24020-141, Niterói, RJ, Brazil. cmronconi@id.uff.br., Guedes GP; Departamento de Química Inorgânica, Universidade Federal Fluminense (UFF), Outeiro de São João Batista, s/n, Campus do Valonguinho, Centro, 24020-141, Niterói, RJ, Brazil. cmronconi@id.uff.br., Nunes WC; Instituto de Física, Universidade Federal Fluminense (UFF), Niterói, RJ, 24210-346, Brazil., Ronconi CM; Departamento de Química Inorgânica, Universidade Federal Fluminense (UFF), Outeiro de São João Batista, s/n, Campus do Valonguinho, Centro, 24020-141, Niterói, RJ, Brazil. cmronconi@id.uff.br.
Jazyk: angličtina
Zdroj: Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2021 Nov 02; Vol. 50 (42), pp. 15003-15014. Date of Electronic Publication: 2021 Nov 02.
DOI: 10.1039/d1dt01961a
Abstrakt: Herein a 1D Co(II) coordination polymer of formula [Co(η 1 -L1)(η 2 -L1)(py) 2 (H 2 O)] n (CoCP) has been synthesised using the rigid H2L1 proligand, containing a long spacer bearing two triple bonds. Single-crystal X-ray diffraction showed that Co(II) adopts a distorted octahedral geometry. The state-averaged complete active self-consistent field (SA-CASSCF) calculation showed that the ground state of CoCP is a high spin quartet with a highly multiconfigurational character of its electronic structure. Due to the large intra- and intermolecular distances between the spin carriers, the magnetic interactions are negligible and the zero-field splitting (ZFS) effects of cobalt(II) ions are predominant. This behavior was confirmed by direct current (DC) magnetic measurements and theoretical calculations using the broken-symmetry approach. Quantum chemical calculations indicate that CoCP has a negative axial component possessing mixed tri-axial anisotropy. The DC magnetic susceptibility data were fitted with a Griffith-Figgis Hamiltonian and the obtained parameters are in good agreement with those simulated by the ab initio calculation. Alternating current (AC) magnetic measurements showed a field induced slow magnetic relaxation in CoCP, which is attributed to the hyperfine interaction effects.
Databáze: MEDLINE
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