Field-induced slow relaxation of magnetization in a tetrahedral Co(ii) complex with easy plane anisotropy

Abstract

The mononuclear Co(II) complex dmphCoBr (dmph = 2,9-dimethyl-1,10-phenanthroline) was obtained and X-ray structurally characterized as a distorted tetrahedron environment that is responsible for the moderately strong positive anisotropy of high spin Co(II). In combination with variable-field magnetic susceptibility data at low temperature, high-field electron paramagnetic resonance (HF-EPR) spectroscopy reveals the presence of easy-plane anisotropy (D > 0) in complex dmphCoBr. Slow magnetic relaxation effects were observed for dmphCoBr in the presence of a dc magnetic field. At very low temperatures, ac magnetic susceptibility data show the magnetic relaxation time, τ, to be temperature-independent, while above 2.4 K thermally activated Arrhenius behavior is dominated with U_eff = 22.8(8) cm⁻¹ and τ₀ = 3.7(5) × 10⁻¹⁰ s. Upon dilution of the complex within a matrix of the isomorphous compound dmphZnBr, ac susceptibility data reveal the individual molecular nature of the slow magnetic relaxation and indicate that the quantum tunneling pathway observed at low temperatures is likely mediated by intermolecular dipolar interactions.