π–π Stacking and magnetic coupling mechanism on a mono-nuclear Mn(II) complex

A novel magnetic coupling is observed in a unpublished crystal that consists of a mono-nuclear manganese(II) complex, namely, [Mn(DPP)(NCS)2] (DPP = 2-(3,5-dimethyl-1H-pyrazol-1-yl)-1,10-phenanthroline), in which neutral DPP molecule functions as tridentate chelated ligand. In the complex Mn(II) ion assumes a distorted trigonal bipyramidal geometry and in the crystal there is a π–π stacking interaction between the adjacent complexes, which involves pyridyl ring and the symmetry-related pyrazolyl ring and pyridyl ring. The fitting for the data of the variable-temperature magnetic susceptibilities with infinite uniform Mn(II) chain formula gave the magnetic coupling constant J = −0.11 cm−1, and theoretical calculations reveal that there exists a very weak anti-ferromagnetic coupling between the adjacent Mn(II) ions with J = −0.02 cm−1. The magnetic coupling sign is explained based on McConnell I spin-polarization mechanism with the analysis of the spin density population and the factors that dominate the magnetic coupling magnitude.