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Open AccessArticle

High-Temperature Cooperative Spin Crossover Transitions and Single-Crystal Reflection Spectra of [FeIII(qsal)2](CH3OSO3) and Related Compounds

1
Department of Chemistry, Graduate School of Science, Kobe University, 1-1 Rokkodai, Nada-ku, Kobe, Hyogo 657-8501, Japan
2
Department of Applied Physics, Okayama University of Science, 1-1 Ridaicho, Kita-ku, Okayama, Okayama 700-0005, Japan
3
Department of Chemistry, Graduate School of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan
4
Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan
5
Institute for Solid State Physics, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8581, Japan
*
Author to whom correspondence should be addressed.
Crystals 2019, 9(2), 81; https://doi.org/10.3390/cryst9020081
Received: 22 January 2019 / Revised: 30 January 2019 / Accepted: 30 January 2019 / Published: 2 February 2019
(This article belongs to the Special Issue Synthesis and Applications of New Spin Crossover Compounds)
New Fe(III) compounds from qsal ligand, [Fe(qsal)2](CH3OSO3) (1) and [Fe(qsal)2](CH3SO3)·CH3OH (3), along with known compound, [Fe(qsal)2](CF3SO3) (2), were obtained as large well-shaped crystals (Hqsal = N-(8-quinolyl)salicylaldimine). The compounds 1 and 2 were in the low-spin (LS) state at 300 K and exhibited a cooperative spin crossover (SCO) transition with a thermal hysteresis loop at higher temperatures, whereas 3 was in the high-spin (HS) state below 300 K. The optical conductivity spectra for 1 and 3 were calculated from the single-crystal reflection spectra, which were, to the best of our knowledge, the first optical conductivity spectra of SCO compounds. The absorption bands for the LS and HS [Fe(qsal)2] cations were assigned by time-dependent density functional theory calculations. The crystal structures of 1 and 2 consisted of a common one-dimensional (1D) array of the [Fe(qsal)2] cation, whereas that of 3 had an unusual 1D arrangement by π-stacking interactions which has never been reported. The crystal structures in the high-temperature phases for 1 and 2 indicate that large structural changes were triggered by the motion of counter anions. The comparison of the crystal structures of the known [Fe(qsal)2] compounds suggests the significant role of a large non-spherical counter-anion or solvate molecule for the total lattice energy gain in the crystal of a charged complex. View Full-Text
Keywords: spin crossover; Fe(III) complex; qsal ligand; thermal hysteresis; structure phase transition; counter-anion; solvate; lattice energy; optical conductivity spectrum spin crossover; Fe(III) complex; qsal ligand; thermal hysteresis; structure phase transition; counter-anion; solvate; lattice energy; optical conductivity spectrum
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MDPI and ACS Style

Takahashi, K.; Yamamoto, K.; Yamamoto, T.; Einaga, Y.; Shiota, Y.; Yoshizawa, K.; Mori, H. High-Temperature Cooperative Spin Crossover Transitions and Single-Crystal Reflection Spectra of [FeIII(qsal)2](CH3OSO3) and Related Compounds. Crystals 2019, 9, 81.

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