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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.

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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.

Item Type: Journal Article
Copyright Holders: 2012 Wiley-VCH
ISSN: 1521-3765
Keywords: crystal engineering; hydrogen bonding; manganese; spin crossover; temperature modulation
Academic Unit/Department: Science > Life, Health and Chemical Sciences
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Item ID: 34408
Depositing User: Charlie Harding
Date Deposited: 25 Oct 2012 08:02
Last Modified: 18 Jan 2016 15:41
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