Enantiomeric Ratio Modulates Hierarchical Networks and Rheological Performance in Cyclohexane Bisurea Supramolecular Gels

This study presents an enantiomeric-ratio-driven strategy for constructing mechanically robust supramolecular gels using cyclohexane bisurea derivatives. By employing non-equimolar enantiomeric mixtures, we achieved an ultralow critical gelation concentration (CGC < 2 mg/mL) in toluene, representing a reduction of more than fivefold compared to homochiral single-enantiomer systems. Rheological measurements revealed substantially enhanced mechanical properties in the non-equimolar gels, with yield stress and storage modulus values up to 17 and 20 times higher, respectively, than those of single-enantiomer gels. Morphological analyses (SEM and POM) indicated that pure enantiomers form isolated crystalline fibers with limited connectivity, whereas racemic mixtures yield disordered amorphous aggregates. In contrast, non-equimolar mixtures self-assemble into hierarchical “sea urchin-like” architectures, wherein crystalline fibers radiate from central cores to form densely interconnected networks. This unique structural motif underpins both the ultralow CGC and superior mechanical performance. Complementary FT-IR, XRD, and DSC analyses demonstrated that chiral imbalance modulates hydrogen-bonding interactions and structural order, while molecular dynamics (MD) simulations provided insight into the divergent self-assembly pathways among homochiral, racemic, and non-equimolar systems. This work provides a stereochemically guided approach for designing high-performance supramolecular gels with tailored hierarchical structures and enhanced functionality.