Nonpolar-to-Polar Phase Transition of a Chiral Ionic Plastic Crystal and Switch of the Rotation Symmetry

Masaya Matsuki, Teppei Yamada, Nobuhiro Yasuda, Shun Dekura, Hiroshi Kitagawa, Nobuo Kimizuka

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The synthesis of a new ionic plastic crystal, tetraethylammonium-d20 d-10-camphorsulfonate, is reported. The crystal has three solid phases, the structures of which were determined by single-crystal X-ray diffraction (XRD). XRD analysis revealed a phase transition from nonpolar space group P21212 to polar space group P21 with increasing temperature. The dynamics of the d-10-camphorsulfonate anion and the tetraethylammonium-d20 cation was investigated by variable-temperature 1H and 2H solid-state NMR spectroscopy. The anion showed swing motion in high-temperature phases, which is in good agreement with the disorder observed in XRD analysis. The cation showed uniaxial rotation even in the low-temperature phase. The rotation axis of the tetrahedral structure showed a transition from the two-fold axis to the three-fold axis with the phase transition.

Original languageEnglish
Pages (from-to)291-297
Number of pages7
JournalJournal of the American Chemical Society
Volume140
Issue number1
DOIs
Publication statusPublished - Jan 10 2018

Fingerprint

Phase Transition
Crystal symmetry
Plastics
Phase transitions
Switches
X-Ray Diffraction
Crystals
Temperature
Tetraethylammonium
X ray diffraction analysis
Anions
Cations
Negative ions
Positive ions
Nuclear magnetic resonance spectroscopy
Magnetic Resonance Spectroscopy
Single crystals
X ray diffraction

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Nonpolar-to-Polar Phase Transition of a Chiral Ionic Plastic Crystal and Switch of the Rotation Symmetry. / Matsuki, Masaya; Yamada, Teppei; Yasuda, Nobuhiro; Dekura, Shun; Kitagawa, Hiroshi; Kimizuka, Nobuo.

In: Journal of the American Chemical Society, Vol. 140, No. 1, 10.01.2018, p. 291-297.

Research output: Contribution to journalArticle

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AU - Kimizuka, Nobuo

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AB - The synthesis of a new ionic plastic crystal, tetraethylammonium-d20 d-10-camphorsulfonate, is reported. The crystal has three solid phases, the structures of which were determined by single-crystal X-ray diffraction (XRD). XRD analysis revealed a phase transition from nonpolar space group P21212 to polar space group P21 with increasing temperature. The dynamics of the d-10-camphorsulfonate anion and the tetraethylammonium-d20 cation was investigated by variable-temperature 1H and 2H solid-state NMR spectroscopy. The anion showed swing motion in high-temperature phases, which is in good agreement with the disorder observed in XRD analysis. The cation showed uniaxial rotation even in the low-temperature phase. The rotation axis of the tetrahedral structure showed a transition from the two-fold axis to the three-fold axis with the phase transition.

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