Non-Heisenberg magnetic behavior of a triangular bridged heterometallic Fe2(III)Co(II) complex: Evidence of strong orbital contributions

Abstract

We report the synthesis, magnetization and ac susceptibility of the triangular μ3-oxo-bridged heterometallic complex [Fe2CoO(CH3COO)6(3-Cl-Py)3], in powder form. The model Hamiltonian is elaborated involving isotropic exchange interactions Fe(III)-Fe(III) and Co(II)-Fe(III) dealing with the real spins of high-spin Co(II) and Fe(III) ions, and also spin-orbit coupling and low-symmetry crystal field (C2v) acting within the T1g4 ground manifold of Co(II) ion. The outlined general model takes into account strong anisotropic orbital contribution to the magnetic characteristics of the whole system arising from Co(II) ion with unquenched orbital angular momentum. The treatment of the Hamiltonian is performed with the use of the irreducible tensor operator technique. The influence of the exchange and spin-orbital interactions on the magnetic properties of Fe2(III)Co(II) clusters is revealed. The result of calculations in the framework of the isotropic model (neglecting low-symmetry crystal field) are in a good agreement with the experimentally observed magnetization versus magnetic field, as well as with the unusual temperature behavior of the magnetic susceptibility of the powder samples (1.8–250 K). The states of the system are enumerated by the quantum number of the total angular momentum J, these hybrid states are combined from the sets of full and intermediate spins of Fe2Co triangle and orbital angular momentum of Co(II), (with fictious L=1). The best fit to the experimental data is achieved for the exchange parameters JFe-Fe=−87.5 cm−1, JFe-Co=−17 cm−1 and orbital reduction factor for Co(II) ion κ=0.93. The ground state and the first excited one are found to possess total angular momentum J=1/2, Effective g-factors for the ground- and first-excited states calculated using the hybrid spin-orbital functions prove to be 4.3 and 0.75, that are distinctly different from the pure spin value 2 peculiar for the Heisenberg model. The comparison of the magnetic measurements with the theory clearly demonstrates the insufficiency of a simple Heisenberg spin-coupling model as evidenced by the discovered strong orbital magnetic contribution.