Syntheses, crystal structures and magnetic properties of two mixed-valence Co(iii)Co(ii) compounds derived from Schiff base ligands: field-supported single-ion-magnet behavior with easy-plane anisotropy

Abstract

Two μ-phenoxo-μ_1,1-azide dinuclear Co^IIICo^II complexes [Co^III(N₃)₂L¹(μ_1,1-N₃)Co^II(N₃)]·MeOH (1) and [Co^III(N₃)₂L²(μ_1,1-N₃)Co^II(N₃)]·MeOH (2) (HL¹ and HL² are two Schiff base ligands having N₂O–N₂O compartments) both possess one hexacoordinate Co(III) and one pentacoordinate Co(II) center. DC magnetic susceptibility and magnetization measurements show an appreciable amount of positive magnetic anisotropy (D/hc ∼ 40 cm⁻¹) that is also confirmed by ab initio CASSCF calculations. AC susceptibility measurements of 1 reveal that it exhibits a slow magnetic relaxation with two relaxation channels. The external magnetic field supports the low-frequency (LF) channel that escapes on heating more progressively than the high-frequency (HF) branch. The relaxation time is as slow as τ = 255 ms at T = 1.9 K and B_DC = 0.6 T, where the LF mole fraction is 69%. The complex 2 also displays similar field-supported slow magnetic relaxation with two relaxation channels.