Magneto-structural correlation of hexakis-dmso cobalt(ii) complex

Abstract

The magnetostructural correlation of the hexakis-dmso cobalt(ii) complex, [Co(dmso)](BPh) (dmso: dimethylsulfoxide), was investigated by single-crystal X-ray diffraction study and magnetic measurements. The magnetic analysis concluded the negative Δ value (H = Δ(L - 2/3) + E(L - L) - (3/2)κλL·S + β[-(3/2)κL + gS]·H (u = x, y, z)), and this was explained by the tetragonal elongation of the octahedral geometry. The magnetostructural correlation was ascertained by both the angular overlap model calculation and the density functional theory calculation.

Magneto-Structural Relationship of Tetragonally-Compressed Octahedral Iron(II) Complex Surrounded by a pseudo-S6 Symmetric Hexakis-Dimethylsulfoxide Environment

“…The 5 E ground state directly indicated the negative ∆ value, which was consistent with the magnetic measurements. Judging from the negative sign of the ∆ value, the magnetic anisotropy is considered to be uniaxial, and the tetragonal compression axis (z axis) is considered to be the easy axis.In the case of the related cobalt(II) complex, [Co(dmso) 6 ][BPh 4 ] 2[14], tetragonal elongation (along the z axis) was observed, and judging from the large orbital reduction factor, close to the free-ion value, the effect of the dmso π orbitals was thought to be smaller than that in the present iron(II) complex. The pseudo-degenerate (d xz , d yz ) orbitals in the cobalt(II) complex were considered to be higher than the d xy orbital, affording the 4 E ground state.…”

“…In the related iron(II) complex 2, the [Fe(dmso)6] 2+ cation was more symmetrical that in 1, and the cation in 2 exactly belongs to the S6 point group. Each dmso moieti 2 showed the similar disorder at 213 K, suggesting the sulfur-inversion motion in the Among the six dmso moieties of the [Fe(dmso) 6 ] 2+ complex cation in 1, four of them were found to be disordered, suggesting the sulfur-inversion motion as well as the cobalt(II) and zinc(II) derivatives [14,15] [16], and [Fe(dmso) 6 ][BPh 4 ] 2 (1) complexes, the cobalt(II) and zinc(II) complexes form isomorphous crystals, while the iron(II) complex ( 1) is isomorphous to the magnesium (II) complex. In the magnesium (II) complex cation, a tetragonal compression was observed similar to 1.…”

“…Earlier, the crystal structure of [Fe(dmso) 6 ][SnCl 6 ] 2 (2) was reported [12], and phase transition behavior was investigated for [Fe(dmso) 6 ][ClO 4 ] 2 [13], but complex 1 has not been reported so far. Among the six dmso moieties of the [Fe(dmso)6] 2+ complex cation in 1, four of t were found to be disordered, suggesting the sulfur-inversion motion as well as th balt(II) and zinc(II) derivatives [14,15]. Among the crystals of [Co(dmso [16], and [Fe(dmso)6][BPh4]2 (1) complexes cobalt(II) and zinc(II) complexes form isomorphous crystals, while the iron(II) com ( 1) is isomorphous to the magnesium (II) complex.…”

Relationship between Structure and Zero-Field Splitting of Octahedral Nickel(II) Complexes with a Low-Symmetric Tetradentate Ligand

“…The dmso ligand coordinated to the central nickel(II) ion through the oxygen atom, and the sulfur atom was disordered [occupancies: S(1), 0.7757 (19); S(1B), 0.2243 (19)]. This is a typical phenomenon for an oxygen-coordinating dmso ligand due to the sulfur inversion [26,27]. The coordination geometry around the central nickel(II) ion was octahedral with NO 5 donor atoms.…”