Correlating magnetic anisotropy with the subtle coordination geometry variation of a series of cobalt(ii)-sulfonamide...

Systematic substitution on the N-(pyridine-2-ylmethyl)-sulfonamide ligand leads to the subtle variation of the CoN4 coordination geometry in a series of cobalt(ii) complexes sharing the common formula of Co[R1(C6N2H5)R2]2, where R1 = H, R2 = 4-tert-butylphenylsulfonyl (tBuphs) 1, R2 = 5-(dimethylamino)naphthalen-1-ylsulfonyl (DNps) 2, R2 = mesitylsulfonyl (Ms) 3, R2 = tosyl (Tos) 4, and R2 = naphthalen-1-ylsulfonyl (Nps) 5; R1 = Me, R2 = tBuphs 6. Magnetic studies show that the axial zero-field splitting parameter (D) is subtlely correlated with the coordination geometric variation subjected to the peripheral substituted groups. Specifically, the distortion from the ideal tetrahedral geometry (Td symmetry) to the seesaw geometry (D2d symmetry) increases uniaxial magnetic anisotropy. The degree of distortion measured by the continuous symmetry measure (CSM) shows that a narrow interval of CSM (6-7), which corresponds to 14-15 degree deviation from the standard tetrahedron, is ideal for maximising the D value in this coordination geometry, while the direction of the D tensor is less sensitive to such a structural variation.