Probing the Effect of Axial Ligands on Easy-Plane Anisotropy of Pentagonal-Bipyramidal Cobalt(II) Single-Ion Magnets

We herein reported the synthetic, structural, computational, and magnetic studies of four air-stable heptacoordinated mononuclear cobalt­(II) complexes, namely, [CoII(tdmmb)­(H2O)2]­[BF4]2 (1), [CoII(tdmmb)­(CN)2]·2H2O (2), [CoII(tdmmb)­(NCS)2] (3), and [CoII(tdmmb)­(SPh)2] (4) (tdmmb = 1,3,10,12-tetramethyl-1,2,11,12-tetraaza[[3]­(2,6)­pyridino[3]­(2,9)-1,10-phenanthrolinophane-2,10-diene; SPh– = thiophenol anion). Constrained by the rigid pentadentate macrocyclic ligand tdmmb, the CoII centers in all of these complexes are in the heptacoordinated pentagonal-bipyramidal geometry. While the equatorial environments of these complexes remain very similar to each other, the axial ligands are systematically modified from C to N to O to S atoms. Analyses of the magnetic data and the ab initio calculations both reveal large easy-plane magnetic anisotropy (D > 0) for all four complexes. While the experimentally obtained D values do not show any clear tendency when the axial coordinated atoms change from C to N to O atoms (complexes 1–3), the largest value is for the heavier and softer S-atom-coordinated complex 4. Because of significant magnetic anisotropy, all four complexes are field-induced single-ion magnets. This work represents a delicate modification of the magnetic anisotropy by tuning the chemical environment of the metal centers.