Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles

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 À1 in DMSO-d 6 solution (DFT prediction for a model compound in the vacuum: 90-100 kJ mol À1 ). 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 Ia " 3d-type bicontinuous cubic liquid-crystalline mesophases through nanosegregation of the ionic and non-ionic parts. Considering the intrinsic characteristic of Ia " 3d-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.

Hierarchical Chiral Supramolecular Nanoarchitectonics with Molecular Detection: Helical Structure Controls upon Self‐Assembly and Coassembly

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Synergistic Effect of Chiral Nanofibers Amplifying the Orbit Angular Momentum To Enhance Optomagnetic Coupling

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