期刊
CRYSTALS
卷 9, 期 2, 页码 -出版社
MDPI
DOI: 10.3390/cryst9020081
关键词
spin crossover; Fe(III) complex; qsal ligand; thermal hysteresis; structure phase transition; counter-anion; solvate; lattice energy; optical conductivity spectrum
资金
- Ministry of Education, Culture, Sports, Science, and Technology of Japan [18028024, 20110007, 19750107, 25410068]
- Grants-in-Aid for Scientific Research [25410068, 19750107, 18028024] Funding Source: KAKEN
New Fe(III) compounds from qsal ligand, [Fe(qsal)(2)](CH3OSO3) (1) and [Fe(qsal)(2)](CH3SO3)center dot 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 pi-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.
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