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Effects of Big Planar Anions on the Spin Transition of a Mononuclear Manganese(III) Complex with a Hexadentate Schiff‐Base Ligand
Author(s) -
Wang Shi,
Li YongHua,
Huang Wei
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201500024
Subject(s) - chemistry , manganese , schiff base , crystallography , spin crossover , ligand (biochemistry) , ion , magnetic susceptibility , spin transition , crystal structure , paramagnetism , single crystal , inorganic chemistry , stereochemistry , organic chemistry , condensed matter physics , biochemistry , physics , receptor
Two new ion‐pair complexes [Mn(3‐MeO‐sal‐ N ‐1,5,8,12)][Ni(dmit) 2 ] ( 1 ) and [Mn(3‐MeO‐sal‐ N ‐1,5,8,12)][Pt(mnt) 2 ] · 2CH 3 CN ( 2 ), based on the known six‐coordinate mononuclear Schiff‐base manganese(III) spin‐crossover complex [Mn(3‐MeO‐sal‐ N ‐1,5,8,12)]NO 3 , have been synthesized and structurally characterized. Their crystal structures indicate that increasing the size of the anion from NO 3 – to [Pt(mnt) 2 ] – and [Ni(dmit) 2 ] – leads to the dimerization of the cations and formation of alternating cation–anion stacks with loss of the most effective cation–anion interactions; only weak short contacts exist between the cations and anions. Magnetic measurements and variable‐temperature single‐crystal X‐ray crystallography analysis provided firm evidence for spin‐crossover (SCO) effects in 1 . The magnetic susceptibility of compound 2 is typical of a simple paramagnet, and the manganese(III) complex cations remain in the high‐spin state in the temperature range 2–300 K.