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Spin-Crossover Hysteresis of [FeII(LHiPr)2(NCS)2] (LHiPr = N-2-Pyridylmethylene-4-Isopropylaniline) Accompanied by Isopropyl Conformation Isomerism

Department of Engineering Science, The University of Electro-Communications, Chofu, Tokyo 182-8585, Japan
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Academic Editor: Guillem Aromí
Magnetochemistry 2015, 1(1), 17-27; https://doi.org/10.3390/magnetochemistry1010017
Received: 31 October 2015 / Accepted: 16 November 2015 / Published: 20 November 2015
(This article belongs to the Special Issue Spin Crossover (SCO) Research)
[FeII(LHiPr)2(NCS)2] (LHiPr = N-2-pyridylmethylene-4-isopropylaniline) showed an abrupt spin-crossover (SCO) at T1/2↓ = 154 K on cooling and at T1/2↑ = 167 K on heating. The thermal hysteresis with a width of 13 K is related with the structural solid-state phase transition. The space group was unchanged as P21/n with Z = 8, and there are two crystallographically independent molecules in a unit cell at 130 and 180 K. The two iron (II) sites synchronously underwent the SCO. The most drastic structural change across the SCO was found in the conformation isomerization of an isopropyl group. Namely, rotation around the C(sp2)–C(sp3) bond by ca. 120° takes place during the SCO. There is no structural disorder in the high-temperature phase. The thermal hysteresis probably originates in the bulk isomerization requiring considerable activation energy in the crystalline solid. View Full-Text
Keywords: spin crossover; hysteresis; structural phase transition; order-disorder transition; conformational isomer; conformer; spin transition; crystal structure spin crossover; hysteresis; structural phase transition; order-disorder transition; conformational isomer; conformer; spin transition; crystal structure
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Mochida, N.; Kimura, A.; Ishida, T. Spin-Crossover Hysteresis of [FeII(LHiPr)2(NCS)2] (LHiPr = N-2-Pyridylmethylene-4-Isopropylaniline) Accompanied by Isopropyl Conformation Isomerism. Magnetochemistry 2015, 1, 17-27.

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