Stabilizing Differential Interfacial Curvatures by Mismatched Molecular Geometries: Toward Polymers with Percolating...

Soft materials with self-assembled networks possess saddle-shaped interfaces with distributed negative Gaussian curvatures. The ability to stabilize such a geometry is critically important for various applications but can be challenging due to the possibly "deficient" packing of the building blocks. This nontrivial challenge has been manifested, for example, by the limited availability of cross-linkable bicontinuous cubic (Q) liquid crystals (LCs), which can be utilized to fabricate compelling polymers with networked nanochannels uniformly sized at ∼1 nm. Here, we devise a facile approach to stabilizing cross-linkable Q mesophases by leveraging the synergistic self-assembly from pairs of scalably synthesized polymerizable amphiphiles. Hybridization of the molecular geometries by mixing significantly increases the propensity of the local deviations in the interfacial curvature specifically required for Q assemblies. "Normal" (type 1) double gyroid LCs possessing 1 nm ionic channels conforming to minimal surfaces can be formulated by simultaneous hydration of the amphiphile mixtures, as opposed to the formation of hexagonal or lamellar mesophases exhibited by the single-amphiphile systems, respectively. Fixation of the bicontinuous network in polymers via radical polymerization has been efficaciously facilitated by the presence of the bifunctional polymerizable groups in one of the employed amphiphiles. High-fidelity lock-in of the ordered continuous 1 nm channels has been unambiguously confirmed by the observation of single-crystal-like diffraction patterns from synchrotron small-angle X-ray scattering and large-area periodicities by transmission electron microscopy. The produced polymeric materials exhibit the required mechanical integrity as well as chemical robustness in a variety of organic solvents that benefit their practical applications for selective transport of ions and molecules.