Ferroelectric Alkylamide-Substituted Helicene Derivative with Two-Dimensional Hydrogen-Bonding Lamellar Phase

Hayato Anetai; Takashi Takeda; Norihisa Hoshino; Higashi Kobayashi; Nozomi Saito; Masanori Shigeno; Masahiko Yamaguchi; Tomoyuki Akutagawa

doi:10.1021/jacs.8b11222

Ferroelectric Alkylamide-Substituted Helicene Derivative with Two-Dimensional Hydrogen-Bonding Lamellar Phase

J Am Chem Soc. 2019 Feb 13;141(6):2391-2397. doi: 10.1021/jacs.8b11222. Epub 2019 Jan 29.

Authors

Hayato Anetai¹, Takashi Takeda^{1

2}, Norihisa Hoshino^{1

2}, Higashi Kobayashi³, Nozomi Saito³, Masanori Shigeno³, Masahiko Yamaguchi³, Tomoyuki Akutagawa^{1

2}

Affiliations

¹ Graduate School of Engineering , Tohoku University , Sendai 980-8579 , Japan.
² Institute of Multidisciplinary Research for Advanced Materials (IMRAM) , Tohoku University , 2-1-1 Katahira, Aoba-ku , Sendai 980-8577 , Japan.
³ Graduate School of Pharmaceutical Sciences , Tohoku University , Sendai 980-8578 , Japan.

PMID: 30646681
DOI: 10.1021/jacs.8b11222

Abstract

Alkylamide (-CONHC _nH_{2 n+1})-substituted benzene and its pyrene derivatives have shown a discotic hexagonal columnar liquid-crystalline phase through a one-dimensional (1D) intermolecular N-H···O═ hydrogen-bonding interaction, the direction of which is inverted through the application of an alternate current voltage. The polar hydrogen-bonding chains and dipole inversion reveal a ferroelectric polarization-electric field ( P- E) hysteresis curve. Non-π-planar helicene derivatives bearing two -CONHC₁₄H₂₉ chains also indicate a ferroelectric response. The racemic helicene derivative shows a bilayer lamellar liquid-crystal phase within a temperature range of 330-420 K, whereas there is no liquid crystallinity for the optically active derivative because of the different molecular assembly structure. The racemic phase is constructed through a two-dimensional (2D) N-H···O═ hydrogen-bonding network, which shows ferroelectric P- E hysteresis curves at above 340 K. The collective dipole inversion in the 2D layer contributes to the ferroelectricity in the lamellar phase. The remanent polarization ( P_r) of 11.1 μC cm^-2 is about 6 times higher than those of the π-planar benzene- and pyrene-based 1D ferroelectrics. Both the density of the hydrogen-bonding site and the domain orientation in the 2D system are higher than those of the 1D columnar system.