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Lattice Effects on the Spin‐Crossover Profile of a Mononuclear Manganese(III) Cation
Author(s) -
Pandurangan Komala,
Gildea Brendan,
Murray Caroline,
Harding Charles J.,
MüllerBunz Helge,
Morgan Grace G.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201102820
Subject(s) - manganese , spin crossover , crossover , lattice (music) , condensed matter physics , materials science , chemistry , physics , computer science , metallurgy , artificial intelligence , acoustics
Six solvated salts of a mononuclear manganese(III) complex with a chelating hexadentate Schiff base ligand are reported. One member of the series, [MnL]PF 6 . 0.5 CH 3 OH ( 1 ), shows a rare low‐spin (LS) electronic configuration between 10–300 K. The remaining five salts, [MnL]NO 3 ⋅ C 2 H 5 OH ( 2 ), [MnL]BF 4 ⋅C 2 H 5 OH ( 3 ), [MnL]CF 3 SO 3 ⋅C 2 H 5 OH ( 4 ), [MnL]ClO 4 ⋅C 2 H 5 OH ( 5 ) and [MnL]ClO 4 ⋅0.5 CH 3 CN ( 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]PF 6 . 0.5 CH 3 OH 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.