Trigonally Distorted Hexacoordinate Co(II) Single-Ion Magnets

三角扭曲六配位 Co(II) 单离子磁体

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作者:Ivan Nemec, Ondřej F Fellner, Berenika Indruchová, Radovan Herchel

Abstract

By simple reactions involving various cobalt(II) carboxylates (acetate and in situ prepared pivalate and 4-hydroxybenzoate salts) and neocuproine (neo), we were able to prepare three different carboxylate complexes with the general formula [Co(neo)(RCOO)2] (R = -CH3 for 1, (CH3)3C- for 2, and 4OH-C4H6- for 3). The [Co(neo)(RCOO)2] molecules in the crystal structures of 1-3 adopt a rather distorted coordination environment, with the largest trigonal distortion observed for 1, whereas 2 and 3 are similarly distorted from ideal octahedral geometry. The combined theoretical and experimental investigations of magnetic properties revealed that the spin Hamiltonian formalism was not a valid approach and the L-S Hamiltonian had to be used to reveal very large magnetic anisotropies for 1-3. The measurements of AC susceptibility showed that all three compounds exhibited slow-relaxation of magnetization in a weak external static magnetic field, and thus can be classified as field-induced single-ion magnets. It is noteworthy that 1 also exhibits a weak AC signal in a zero-external magnetic field.

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