title: Probing the Effect of Axial Ligands on Easy-Plane Anisotropy of Pentagonal-Bipyramidal Cobalt(II) Single-Ion Magnets.
abstract: 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 CoIIcenters 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.
authors.affiliation: State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, China.
authors.forename: Dong
authors.initials: D
authors.lastname: Shao
authors.affiliation: State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, China.
authors.forename: Shao-Liang
authors.initials: SL
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, China.
authors.forename: Le
authors.initials: L
authors.lastname: Shi
authors.affiliation: Jiangsu Key Laboratory for NSLSCS, School of Physical Science and Technology, Nanjing Normal University , Nanjing 210023, China.
authors.forename: Yi-Quan
authors.initials: YQ
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Coordination Chemistry, Collaborative Innovation Center of Advanced Microstructures, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, China.
authors.forename: Xin-Yi
authors.initials: XY
authors.lastname: Wang