TY - JOUR
T1 - Nonpolar-to-Polar Phase Transition of a Chiral Ionic Plastic Crystal and Switch of the Rotation Symmetry
AU - Matsuki, Masaya
AU - Yamada, Teppei
AU - Yasuda, Nobuhiro
AU - Dekura, Shun
AU - Kitagawa, Hiroshi
AU - Kimizuka, Nobuo
N1 - Funding Information:
This work was partly supported by JST PRESTO Grant No. JPMJPR141D, Japan and JSPS KAKENHI Grant Nos. JP25220805, JP16H06513 (Coordination Asymmetry).
Funding Information:
The result of single-crystal X-ray diffractometry was obtained at BL40XU in SPring-8 (Proposal No. 2015A1143 and 2016A1051). This work was partly supported by JST PRESTO Grant No. JPMJPR141D, Japan, and JSPS KAKENHI Grant Nos. JP25220805, JP16H06513 (Coordination Asymmetry).
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2018/1/10
Y1 - 2018/1/10
N2 - 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.
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.
UR - http://www.scopus.com/inward/record.url?scp=85040325985&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85040325985&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b10249
DO - 10.1021/jacs.7b10249
M3 - Article
C2 - 29200273
AN - SCOPUS:85040325985
VL - 140
SP - 291
EP - 297
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 1
ER -