Lattice Effects on the Spin‐Crossover Profile of a Mononuclear Manganese(III) Cation |
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| Authors: | Dr Komala Pandurangan Brendan Gildea Dr Caroline Murray Dr Charles J Harding Dr Helge Müller‐Bunz Dr Grace G Morgan |
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| Institution: | 1. Centre for Synthesis and Chemical Biology, School of Chemistry and School of Chemistry and Chemical Biology and the SFI‐Strategic Research Cluster in Solar Energy Conversion, University College Dublin, Belfield, Dublin 4 (Ireland), Fax: (+353)?1‐716‐1178;2. Department of Chemistry, The Open University, Walton Hall, Milton Keynes, MK7 6AA (United Kingdom) |
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| 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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| Keywords: | crystal engineering hydrogen bonding manganese spin crossover temperature modulation |
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