TY - JOUR
T1 - Effects of big planar anions on the spin transition of a mononuclear manganese(III) complex with a hexadentate schiff-base ligand
AU - Wang, Shi
AU - Li, Yong Hua
AU - Huang, Wei
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/5/1
Y1 - 2015/5/1
N2 - 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]·2CH3CN (2), based on the known six-coordinate mononuclear Schiff-base manganese(III) spin-crossover complex [Mn(3-MeO-sal-N-1,5,8,12)]NO3, have been synthesized and structurally characterized. Their crystal structures indicate that increasing the size of the anion from NO3- 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 variableerature 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. Spin-crossover in d4 ions is a most rare event. Changing the size of the anion from NO3- to [Pt(mnt)2]- and [Ni(dmit)2]- leads to significant changes in the overall crystal packing of Mn ion-pair complexes and furthermore in the spin state of the MnIII center.
AB - 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]·2CH3CN (2), based on the known six-coordinate mononuclear Schiff-base manganese(III) spin-crossover complex [Mn(3-MeO-sal-N-1,5,8,12)]NO3, have been synthesized and structurally characterized. Their crystal structures indicate that increasing the size of the anion from NO3- 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 variableerature 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. Spin-crossover in d4 ions is a most rare event. Changing the size of the anion from NO3- to [Pt(mnt)2]- and [Ni(dmit)2]- leads to significant changes in the overall crystal packing of Mn ion-pair complexes and furthermore in the spin state of the MnIII center.
KW - Hydrogen bonds
KW - Magnetic properties
KW - Manganese
KW - Spin crossover
UR - http://www.scopus.com/inward/record.url?scp=84928753292&partnerID=8YFLogxK
U2 - 10.1002/ejic.201500024
DO - 10.1002/ejic.201500024
M3 - 文章
AN - SCOPUS:84928753292
SN - 1434-1948
VL - 2015
SP - 2237
EP - 2244
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 13
ER -