The effect of ligands with heavy donor atoms on the magnetic anisotropy of the pseudo-tetrahedral cobalt complexes, Co(quinoline)2I2 (1) and Co(EPh3)2I2 (2-3) (E = P, As) has been investigated. The axial zero-field splitting parameter D was found to vary from +9.2 cm(-1) in 1 to -36.9 cm(-1) in 2 and -74.7 cm(-1) in 3. Compounds 2 and 3 exhibit slow relaxation of the magnetization up to 4 K under an applied dc field, indicating SMM behavior.

Given the recent advent of mononuclear single-molecule magnets (SMMs), a rational approach based on lanthanides with axially elongated f-electron charge cloud (prolate) has only recently received attention. We report herein a new SMM, [Li(THF)4[Er{N(SiMe3)2}3Cl]⋅2 THF, which exhibits slow relaxation of the magnetization under zero dc field with an effective barrier to the reversal of magnetization (ΔEeff/kB =63.3 K) and magnetic hysteresis up to 3 K at a magnetic field sweep rate of 34.6 Oe s(-1). This work questions the theory that oblate or prolate lanthanides must be stabilized with the appropriate ligand framework in order for SMM behavior to be favored.

A trigonal antiprismatic Co(ii) molecule exhibits counterion-dependent relaxation of the magnetization due to the importance of the Raman relaxation process.