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

doi:10.3390/cryst9020081

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

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

10 Citations (Scopus)

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 language	English
Article number	81
Journal	Crystals
Volume	9
Issue number	2
DOIs	https://doi.org/10.3390/cryst9020081
Publication status	Published - 2019

Keywords

Counter-anion
Fe(III) complex
Lattice energy
Optical conductivity spectrum
Qsal ligand
Solvate
Spin crossover
Structure phase transition
Thermal hysteresis

ASJC Scopus subject areas

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

Access to Document

10.3390/cryst9020081

Cite this

Takahashi, K., Yamamoto, K., Yamamoto, T., Einaga, Y., Shiota, Y., Yoshizawa, K., & Mori, H. (2019). High-temperature cooperative spin crossover transitions and single-crystal reflection spectra of [Fe ^III (qsal) ₂ ](CH ₃ OSO ₃ ) and related compounds Crystals, 9(2), Article 81. https://doi.org/10.3390/cryst9020081

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 et al.
In: Crystals, Vol. 9, No. 2, 81, 2019.

Research output: Contribution to journal › Article › peer-review

Takahashi, K, Yamamoto, K, Yamamoto, T , Einaga, Y, Shiota, Y, Yoshizawa, K & Mori, H 2019, ' High-temperature cooperative spin crossover transitions and single-crystal reflection spectra of [Fe ^III (qsal) ₂ ](CH ₃ OSO ₃ ) and related compounds ', Crystals, vol. 9, no. 2, 81. https://doi.org/10.3390/cryst9020081

Takahashi K, Yamamoto K, Yamamoto T , Einaga Y, Shiota Y, Yoshizawa K et al. High-temperature cooperative spin crossover transitions and single-crystal reflection spectra of [Fe ^III (qsal) ₂ ](CH ₃ OSO ₃ ) and related compounds Crystals. 2019;9(2):81. doi: 10.3390/cryst9020081

Takahashi, Kazuyuki ; Yamamoto, Kaoru ; Yamamoto, Takashi et al. / High-temperature cooperative spin crossover transitions and single-crystal reflection spectra of [Fe ^III (qsal) ₂ ](CH ₃ OSO ₃ ) and related compounds In: Crystals. 2019 ; Vol. 9, No. 2.

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

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.",

keywords = "Counter-anion, Fe(III) complex, Lattice energy, Optical conductivity spectrum, Qsal ligand, Solvate, Spin crossover, Structure phase transition, Thermal hysteresis",

author = "Kazuyuki Takahashi and Kaoru Yamamoto and Takashi Yamamoto and Yasuaki Einaga and Yoshihito Shiota and Kazunari Yoshizawa and Hatsumi Mori",

note = "Funding Information: Funding: This research was funded partly by a Grant-in-Aid for Scientific Research on the Priority Area of Molecular Conductors (no. 18028024) and on Innovative Areas of Molecular Degrees of Freedom (no. 20110007), and a Grant-in-Aid for Young Scientists (B) (no. 19750107) and for Scientific Research (C) (no. 25410068) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. Funding Information: This research was funded partly by a Grant-in-Aid for Scientific Research on the Priority Area of Molecular Conductors (no. 18028024) and on Innovative Areas of Molecular Degrees of Freedom (no. 20110007), and a Grant-in-Aid for Young Scientists (B) (no. 19750107) and for Scientific Research (C) (no. 25410068) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. Acknowledgments: K.T. is grateful to T. Ishikawa at Tokyo Institute of Technology for discussing the optical properties of the Fe complexes. K.T. also thanks to A. Sakamoto at the University of Tokyo, and Y. Furuie at Kobe University for performing the elemental analysis. Publisher Copyright: {\textcopyright} 2019 by the authors. Licensee MDPI, Basel, Switzerland.",

year = "2019",

doi = "10.3390/cryst9020081",

language = "English",

volume = "9",

journal = "Crystals",

issn = "2073-4352",

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T1 - High-temperature cooperative spin crossover transitions and single-crystal reflection spectra of [Fe III (qsal) 2 ](CH 3 OSO 3 ) and related compounds

AU - Takahashi, Kazuyuki

AU - Yamamoto, Kaoru

AU - Yamamoto, Takashi

AU - Einaga, Yasuaki

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Mori, Hatsumi

N1 - Funding Information: Funding: This research was funded partly by a Grant-in-Aid for Scientific Research on the Priority Area of Molecular Conductors (no. 18028024) and on Innovative Areas of Molecular Degrees of Freedom (no. 20110007), and a Grant-in-Aid for Young Scientists (B) (no. 19750107) and for Scientific Research (C) (no. 25410068) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. Funding Information: This research was funded partly by a Grant-in-Aid for Scientific Research on the Priority Area of Molecular Conductors (no. 18028024) and on Innovative Areas of Molecular Degrees of Freedom (no. 20110007), and a Grant-in-Aid for Young Scientists (B) (no. 19750107) and for Scientific Research (C) (no. 25410068) from the Ministry of Education, Culture, Sports, Science, and Technology of Japan. Acknowledgments: K.T. is grateful to T. Ishikawa at Tokyo Institute of Technology for discussing the optical properties of the Fe complexes. K.T. also thanks to A. Sakamoto at the University of Tokyo, and Y. Furuie at Kobe University for performing the elemental analysis. Publisher Copyright: © 2019 by the authors. Licensee MDPI, Basel, Switzerland.

PY - 2019

Y1 - 2019

N2 - 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.

AB - 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.

KW - Counter-anion

KW - Fe(III) complex

KW - Lattice energy

KW - Optical conductivity spectrum

KW - Qsal ligand

KW - Solvate

KW - Spin crossover

KW - Structure phase transition

KW - Thermal hysteresis

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U2 - 10.3390/cryst9020081

DO - 10.3390/cryst9020081

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