Theoretical study of the magnetic anisotropy and magnetic tunnelling in mononuclear Ni(II) complexes with potential molecular magnet behavior

Magnetic molecules that present a slow decay of their magnetization (molecular magnets) are very interesting both from a fundamental and applied points of view. While many approaches focus strongly on finding systems with strong magnetic anisotropy giving rise to large spin-reversal barriers, less is known on the behavior of magnetic tunnelling, which is also a fundamental component of molecular magnet behavior. In this work, we propose a model to describe both the spin-reversal barrier and magnetic tunnelling in Ni(II) trigonal bipyramidal complexes, which could be easily extended to other transitionmetal systems. Based on this model, we show the criteria that lead to the optimal complexes to find molecular magnet behavior. We test our proposal with multi-reference configuration-interaction (MRCI) and ligand-field-density-functional-theory (LF-DFT) first-principles calculations applied over several families of mononuclear Ni(II) complexes. As a salient result, we find that the complex [NiCl3(Hdabco)(2)](+) (dabco is 1,4-diazabicyclo[2.2.2]-octane) displays both a very large magnetic anisotropy energy, 524 cm(-1), and a small tunnelling splitting, 0.2 cm(-1), when compared to other systems containing the same metal. We expect molecular magnet behaviour to be observed when small magnetic fields are employed to disrupt tunnelling. These values are reached due to the choice of ligands that favor a complete destruction of the Jahn-Teller distortions through spin-orbit coupling and an unquenched orbital momentum.