Novel cyclodextrin (CD)-based amphiphilic poly­(carboxylic acid)­s that self-assemble into highly ordered smectic liquid crystalline mesophases were investigated as a novel class of protonic conductors. These structurally well-defined materials are synthesized from nontoxic and environment-friendly CDs, which possess a unique face-to-face pseudosymmetry. By taking advantage of such geometry, a series of flexible tetraethylene glycol groups terminated with a carboxylic acid functionality were introduced to the CD’s secondary face, resulting in the formation of long-range 2D hydrogen-bond networks in the smectic mesophases over a wide temperature window. This new material was found to exhibit impressive proton conductivities in solid states, up to 1.4 × 10–2 S cm–1 at 70 °C and 95% humidity. This constitutes the first report of amphiphilic CD-based liquid crystals applied as proton conductive materials.

Inverting the substitution patterns of amphiphilic cyclodextrins has uncovered their unprecedented abilities to form hexagonal columnar mesophases.

A cyano-tetraethylene glycol functionalized amphiphilic cyclodextrin forms liquid crystalline self-assembly that shows promising ion conductivity (Li+).

An ovel familyo fa mphiphilic cyclodextrin(CD)-based liquid crystalst hat bear O-acetylated oligoethyleneg lycol chains at the secondary face is reported. Unlike most of the previously reported liquid crystals (LC) based on chemically modified CDs, which depend on H-bonding as the primary intermolecular forces, the presentC Dd erivatives self-assemble into highly or-dered smecticl iquid crystal phases via the weakerd ipoledipole intermolecular interactions.T he obtained materials are found to display much improved properties such as improved thermostability,r educed clearingt emperatures, and better fluidity.T he present work opens up new possibilities to design CD-based LC materials.