Role of Orbital Degeneracy in the Single Molecule Magnet Behavior of a Mononuclear High-Spin Fe(II) Complex

To explain the single-molecule magnet behavior of the mononuclear complex [(tpaMes)Fe](-) we have developed a model that takes into account the trigonal ligand field splitting of the atomic D-5 term of the Fe(II) ion, and the spin-orbital splitting and mixing of the ligand field terms. The ground ligand field term is shown to be the orbital doublet E-5 possessing an unquenched orbital angular momentum. We demonstrate that the splitting of this term cannot be described by the conventional zero-field splitting Hamiltonian proving thus the irrelevance of the spin-Hamiltonian formalism in the present case. The first-order orbital angular momentum is shown to lead to the strong magnetic anisotropy with the trigonal axis being the easy axis of the magnetization.