Quantifying magnetic anisotropy using X-ray and neutron diffraction

In this work, the magnetic anisotropy in two iso-structural distorted tetrahedral Co(II) complexes, CoX (2)tmtu(2) [X = Cl(1) and Br(2), tmtu = tetra­methyl­thio­urea] is investigated, using a combination of polarized neutron diffraction (PND), very low-temperature high-resolution synchrotron X-ray diffraction and CASSCF/NEVPT2 ab initio calculations. Here, it was found consistently among all methods that the compounds have an easy axis of magnetization pointing nearly along the bis­ector of the compression angle, with minute deviations between PND and theory. Importantly, this work represents the first derivation of the atomic susceptibility tensor based on powder PND for a single-molecule magnet and the comparison thereof with ab initio calculations and high-resolution X-ray diffraction. Theoretical ab initio ligand field theory (AILFT) analysis finds the d (xy) orbital to be stabilized relative to the d (xz) and d (yz) orbitals, thus providing the intuitive explanation for the presence of a negative zero-field splitting parameter, D, from coupling and thus mixing of d (xy) and [Image: see text]. Experimental d-orbital populations support this interpretation, showing in addition that the metal–ligand covalency is larger for Br-ligated 2 than for Cl-ligated 1.