Challenges in assignment of orbital populations in a high spin manganese(III) complex

Magnetic, structural and computational data of four complex salts with the same mononuclear high spin octahedral Mn(iii) complex cation are reported. The manifestation of Jahn-Teller-like distortions in the Mn(iii) cation is dependent on the nature of the charge-balancing anion, with small anions yielding a planar elongation and large anions freezing out a preferential axial elongation along one of the amine-Mn-imine directions within that same plane. Modulation of the lattice by changing the charge balancing anion results in mixing of the orbital symmetry due to vibrational perturbation.