Lattice effects on the spin-crossover profile of a mononuclear manganese(III) cation

Pandurangan, K.; Gildea, B.; Murray, C.; Harding, C. J.; Müller-Bunz, H. and Morgan, G. G. (2012). Lattice effects on the spin-crossover profile of a mononuclear manganese(III) cation. Chemistry - A European Journal, 18(7) pp. 2021–2029.

DOI: https://doi.org/10.1002/chem.201102820

Abstract

Six solvated salts of a mononuclear manganese(III) complex with a chelating hexadentate Schiff base ligand are reported. One member of the series, [MnL]PF₆.0.5 CH₃OH (1), shows a rare low-spin (LS) electronic configuration between 10–300 K. The remaining five salts, [MnL]NO₃⋅ C₂H₅OH (2), [MnL]BF₄⋅C₂H₅OH (3), [MnL]CF₃SO₃⋅C₂H₅OH (4), [MnL]ClO₄⋅C₂H₅OH (5) and [MnL]ClO₄⋅0.5 CH₃CN (6), all show gradual incomplete spin-crossover (SCO) behaviour. The structures of all were determined at 100 K, and also at 293 K in the case of 3–6. The LS salt [MnL]PF₆.0.5 CH₃OH is the only member of the series that does not exhibit strong hydrogen bonding. At 100 K two of the four SCO complexes (2 and 4) assemble into 1D hydrogen-bonded chains, which weaken or rupture on warming. The remaining SCO complexes 3, 5 and 6 do not form 1D hydrogen-bonded chains, but instead exhibit discrete hydrogen bonding between cation/counterion, cation/solvent or counterion/solvent and show no significant change on warming.

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