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, [Co-II(tdmmb)(H2O)(2)][BF4](2) (1)) [COII(tdMMb)(CN)(2)]center dot 2H(2)O (2), [Co-II(tdmrrib)(NCS)(2)] (3), and [Co-II(tdmmb)(SPh)(2)] (4) (tdmmb = 1,3,10,12-tetramethy1-1,2,11,12-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 Co-II 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.