Origin of the zero-field splitting in mononuclear octahedral dihalide MnII complexes: an investigation by multifrequency high-field electron paramagnetic resonance and density functional theory

The synthesis, structural characterization, and electronic properties of a new series of high-spin six-coordinate dihalide mononuclear MnII complexes [Mn(tpa)X2] (tpa=tris-2-picolylamine; X=I (1), Br (2), and Cl (3)) are reported. The analysis of the crystallographic data shows that in all investigated complexes the manganese ion lies in the center of a distorted octahedron with a cis configuration of the halides imposed by the tpa ligand. By a multifrequency high-field electron paramagnetic resonance investigation (95-285 GHz), the electronic properties of 1-3 were determined (DI=-0.600, DBr=-0.360, DCl=+0.115 cm-1), revealing the important effect of (i) the nature of the halide and (ii) the configuration (cis/trans) of the two halides on the magnitude of D. The spin Hamiltonian parameters obtained by density functional theory calculations initiated from the crystal structure of 1-3 are in reasonable agreement with the experimental values. The absolute value of D is consistently overestimated, but the sign and the trend over the chemical series is well reproduced. Theoretical models (cis- and trans-[Mn(NH3)4X2], X=I, Br, Cl and F) have been used to investigate the different contributions to D and also to understand the origin of the experimentally observed changes in D within the series reported here. This study reveals that the spin-spin coupling contributions to the D tensor are non-negligible for the lighter halides (F, Cl) but become insignificant for the heavier halides (I, Br). The four different types of excitations involved in the spin-orbit coupling (SOC) part of the D tensor contribute with comparable magnitudes and opposing signs. The general trend observed for halide MnII complexes (DI>DBr>DCl) can be explained by the fact that the halide SOC dominates the D value in these systems with a major contribution arising from interference between metal- and halide-SOC contributions, which are proportional to the product of the SOC constants of Mn and X.