Spin State Solvomorphism in a Series of Rare S = 1 Manganese(III) Complexes

Structural, magnetic and spectroscopic data of four complex salts, [Mn(napsal2323)]NTf2, 1,[Mn(napsal2323)]ClO4, 2, [Mn(napsal2323)]BF4, 3 and Mn(napsal2323)]NO3, 4, of the [Mn(napsal2323)]+ complex cation indicate that the Mn3+ ion is stabilized in the rare S = 1 spin triplet form in this ligand sphere. Zero-field splitting values of D = +19.6 cm-1 and |E| = 2.02 cm-1for complex 1 were obtained by High Field Electron Paramagnetic Resonance (HFEPR) measurements conducted over a range of frequencies and field strengths. Structural and magnetic data also indicate that co-crystallization of complexes 2 and 3 with 0.5 equivalents of ethanol yields the high spin S = 2 forms of the perchlorate and tetrafluoroborate solvates [Mn(napsal2323)]ClO4•0.5(C2H5OH), 2•0.5EtOH and [Mn(napsal2323)]BF4•0.5(C2H5OH), 3•0.5EtOH.