Double-Gyroid Nanostructure Formation by Aggregation-Induced Atropisomerization and Co-Assembly of Ionic Liquid-Crystalline Amphiphiles |
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Authors: | Nanami Uemura Tsubasa Kobayashi Shintaro Yoshida Ya-xin Li Karel Goossens Xiangbing Zeng Go Watanabe Takahiro Ichikawa |
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Affiliation: | 1. Department of Biotechnology, Tokyo University of Agriculture and Technology, Tokyo, 184-8588 Japan;2. Department of Physics, School of Science, Kitasato University, Sagamihara, Kanagawa, 252-0373 Japan;3. Department of Materials Science and Engineering, University of Sheffield, Sheffield, S1 3JD UK;4. Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), Ulsan, 44919 Republic of Korea |
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Abstract: | We report a new molecular-design principle for creating double-gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol−1 in DMSO-d6 solution (DFT prediction for a model compound in the vacuum: 90–100 kJ mol−1). Due to the restricted rotation, the amphiphiles feature “double” atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co-organize into -type bicontinuous cubic liquid-crystalline mesophases through nanosegregation of the ionic and non-ionic parts. Considering the intrinsic characteristic of -type bicontinuous cubic structures that they are composed of intertwined right- and left-handed single gyroids, we propose that the simultaneous presence of both R- and S-atropisomers is an important contributor to the formation of double-gyroid structures. |
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Keywords: | atropisomers bicontinuous cubic phase double-gyroid structures liquid crystals self-organization |
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