Single-Component Gyroid Formation and Membrane Fabrication from Imidazolium Gemini Zwitterionic Amphiphiles with Fluorinated Anions.

We report the design and self-assembly of amphiphilic imidazolium-based gemini zwitterions with fluorinated anions (ImGZI-TFSI) that form stable gyroid phases via liquid-crystalline (LC) organization under additive-free conditions. By tuning their surfactant chain length and introducing cross-linkable diene groups, we achieved precise morphological control and fabricated free-standing polymer membranes using Diene-C16ImGZI-TFSI. In contrast, the incorporation of diene groups into an analogue with shorter surfactant chains of C14 disrupted gyroid order, which was subsequently restored by lithium chloride (LiCl) addition. These findings highlight the critical role of intermolecular interactions and molecular packing efficiency in LC self-assembly, enabling the design strategy of additive-free, cross-linkable zwitterionic gyroid polymer membranes with potential applications in functional nanostructured materials.