Magnetostructural D-Correlations and Their Impact on Single-Molecule Magnetism

Functional dependence of the axial zero-field splitting parameter D with respect to a properly chosen geometrical parameter (Dstr) in metal complexes is termed the magnetostructural D-correlation. In mononuclear hexacoordinate Ni(II) complexes with the ground electronic term 3B1g (3A2g in the regular octahedron), it proceeds along two intercepting straight lines, allowing for predicting the sign and magnitude of the D-parameter by knowing the X-ray structure alone; Dstr is constructed from the metal–ligand bond lengths. In hexacoordinate Co(II) complexes, it is applicable only in the segment of the compressed bipyramid where the ground electronic term 4B1g is orbitally non-degenerate so that the spin Hamiltonian formalism holds true. The D vs. Dstr correlation is strongly non-linear, and it is represented by a set of decreasing exponentials. In tetracoordinate Co(II) complexes, on the contrary, the angular distortion from the regular tetrahedron is crucial so that the appropriate structural parameter Dstr is constructed of bond angles. The most complex case is represented by pentacoordinated Co(II) systems, for which it is not yet possible to define a statistically significant correlation. All of these empirical correlations originate in the electronic structure of metal complexes that can be modelled using generalized crystal-field theory. As the barrier to spin reversal in single-molecule magnets is proportional to the D-value, for rational tuning and/or prediction of the single-molecule magnetic behaviour, knowledge/prediction of the D-parameter is beneficial. In this review, we present the statistical processing of an extensive set of structural and magnetic data on Co(II) and Ni(II) complexes, which were published over the past 15 years. Magnetostructural D-correlations defined for this data set are reviewed in detail.