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Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles
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...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7318300/ https://www.ncbi.nlm.nih.gov/pubmed/32128958 http://dx.doi.org/10.1002/anie.202000424 |
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author | Uemura, Nanami Kobayashi, Tsubasa Yoshida, Shintaro Li, Ya‐xin Goossens, Karel Zeng, Xiangbing Watanabe, Go Ichikawa, Takahiro |
author_facet | Uemura, Nanami Kobayashi, Tsubasa Yoshida, Shintaro Li, Ya‐xin Goossens, Karel Zeng, Xiangbing Watanabe, Go Ichikawa, Takahiro |
author_sort | Uemura, Nanami |
collection | PubMed |
description | 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‐d(6) 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 [Formula: see text] ‐type bicontinuous cubic liquid‐crystalline mesophases through nanosegregation of the ionic and non‐ionic parts. Considering the intrinsic characteristic of [Formula: see text] ‐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. |
format | Online Article Text |
id | pubmed-7318300 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-73183002020-06-29 Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles Uemura, Nanami Kobayashi, Tsubasa Yoshida, Shintaro Li, Ya‐xin Goossens, Karel Zeng, Xiangbing Watanabe, Go Ichikawa, Takahiro Angew Chem Int Ed Engl Communications 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‐d(6) 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 [Formula: see text] ‐type bicontinuous cubic liquid‐crystalline mesophases through nanosegregation of the ionic and non‐ionic parts. Considering the intrinsic characteristic of [Formula: see text] ‐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. John Wiley and Sons Inc. 2020-03-17 2020-05-25 /pmc/articles/PMC7318300/ /pubmed/32128958 http://dx.doi.org/10.1002/anie.202000424 Text en © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Uemura, Nanami Kobayashi, Tsubasa Yoshida, Shintaro Li, Ya‐xin Goossens, Karel Zeng, Xiangbing Watanabe, Go Ichikawa, Takahiro Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles |
title | Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles |
title_full | Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles |
title_fullStr | Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles |
title_full_unstemmed | Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles |
title_short | Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles |
title_sort | double‐gyroid nanostructure formation by aggregation‐induced atropisomerization and co‐assembly of ionic liquid‐crystalline amphiphiles |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7318300/ https://www.ncbi.nlm.nih.gov/pubmed/32128958 http://dx.doi.org/10.1002/anie.202000424 |
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