Theoretical Modeling of the Magnetic Behavior of Thiacalix[4]arene Tetranuclear Mn^II₂Gd^III₂ and Co^II₂Eu^III₂ Complexes

In view of a wide perspective of 3d-4f complexes in single-molecule magnetism, here we propose an explanation of the magnetic behavior of the two thiacalix[4]arene tetranuclear heterometallic complexes Mn^II₂Gd^III₂ and Co^II₂Eu^III₂. The energy pattern of the Mn^II₂Gd^III₂ complex evaluated in the framework of the isotropic exchange model exhibits a rotational band of the low-lying spin excitations within which the Landé intervals are affected by the biquadratic spin-spin interactions. The nonmonotonic temperature dependence of the χT product observed for the Mn^II₂Gd^III₂ complex is attributed to the competitive influence of the ferromagnetic Mn-Gd and antiferromagnetic Mn-Mn exchange interactions, the latter being stronger (J(Mn, Mn) = -1.6 cm^-1, J_s(Mn, Gd) = 0.8 cm^-1, g = 1.97). The model for the Co^II₂Eu^III₂ complex includes uniaxial anisotropy of the seven-coordinate Co^II ions and an isotropic exchange interaction in the Co^II₂ pair, while the Eu^III ions are diamagnetic in their ground states. Best-fit analysis of χT versus T showed that the anisotropic contribution (arising from a large zero-field splitting in Co^II ions) dominates (weak-exchange limit) in the Co^II₂Eu^III₂ complex (D = 20.5 cm^-1, J = -0.4 cm^-1, g_Co = 2.22). This complex is concluded to exhibit an easy plane of magnetization (arising from the Co^II pair). It is shown that the low-lying part of the spectrum can be described by a highly anisotropic effective spin-¹/₂ Hamiltonian that is deduced for the Co^II₂ pair in the weak-exchange limit.