Uemura, N., Kobayashi, T., Yoshida, S. et al. (5 more authors) (2020) Double gyroid nanostructure formation by aggregation‐induced atropisomerization and co‐assembly of ionic liquid‐crystalline amphiphiles. Angewandte Chemie International Edition, 59 (22). pp. 8445-8450. ISSN 1433-7851
Abstract
Herein we report a new molecular design principle for creating double gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings in close proximity to one another 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‐ d 6 solution. DFT calculations predicted an activation energy of 90–100 kJ mol –1 in vacuum for a model compound. Due to the restricted rotation, the amphiphiles feature “double” atropisomeric axes in their ionic segments and form three stable atropisomers, namely: meso, R and S . We found that these isomers co‐organize into Ia Common.EditSubmissionSteps.Transform.EquationText d ‐type bicontinuous cubic liquid‐crystalline mesophases through nanosegregation of the ionic and non‐ionic parts, respectively. Considering the intrinsic characteristic of Ia Common.EditSubmissionSteps.Transform.EquationText d ‐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.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, (http://creativecommons.org/licenses/by/4.0/) which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
Keywords: | Atropisomerization; Double Gyroid; liquid crystal; Bicontinuous Cubic Phase; self-assembly |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Engineering (Sheffield) > Department of Materials Science and Engineering (Sheffield) |
Funding Information: | Funder Grant number ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/P002250/1 ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/T003294/1 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 13 Mar 2020 10:30 |
Last Modified: | 06 Dec 2021 17:20 |
Status: | Published |
Publisher: | Wiley |
Refereed: | Yes |
Identification Number: | 10.1002/anie.202000424 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:158337 |