High-temperature cooperative spin crossover transitions and single-crystal reflection spectra of [Fe III (qsal) 2 ](CH 3 OSO 3 ) and related compounds

Kazuyuki Takahashi, Kaoru Yamamoto, Takashi Yamamoto, Yasuaki Einaga, Yoshihito Shiota, Kazunari Yoshizawa, Hatsumi Mori

Research output: Contribution to journalArticle

Abstract

New Fe(III) compounds from qsal ligand, [Fe(qsal) 2 ](CH 3 OSO 3 ) (1) and [Fe(qsal) 2 ](CH 3 SO 3 )·CH 3 OH (3), along with known compound, [Fe(qsal) 2 ](CF 3 SO 3 ) (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.

Original languageEnglish
Article number81
JournalCrystals
Volume9
Issue number2
DOIs
Publication statusPublished - Jan 1 2019

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OSO-3
Optical conductivity
crossovers
Crystal structure
Single crystals
methylidyne
Anions
Cations
single crystals
Negative ions
Positive ions
Crystals
Hysteresis loops
Crystal lattices
Temperature
crystal structure
Density functional theory
Absorption spectra
counters
Ligands

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Inorganic Chemistry

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High-temperature cooperative spin crossover transitions and single-crystal reflection spectra of [Fe III (qsal) 2 ](CH 3 OSO 3 ) and related compounds . / Takahashi, Kazuyuki; Yamamoto, Kaoru; Yamamoto, Takashi; Einaga, Yasuaki; Shiota, Yoshihito; Yoshizawa, Kazunari; Mori, Hatsumi.

In: Crystals, Vol. 9, No. 2, 81, 01.01.2019.

Research output: Contribution to journalArticle

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