Symmetry Breaking in the Supramolecular Gels of an Achiral Gelator Exclusively Driven by π-π Stacking

Supramolecular symmetry breaking, in which chiral assemblies with imbalanced right- and left-handedness emerge from achiral molecular building blocks, has been achieved in the organogels of a C-3-symmetric molecule only via pi-pi stacking. Specifically, an achiral C3-symmetric benzene-1,3,5-tricarboxylate substituted with methyl cinnamate through ester bond was found to form organogels in various organic solvents. More interestingly, when gels formed in cyclohexane, symmetry breaking occurred; i.e., optically active organogels together with the helical nanofibers with predominant handedness were obtained. Furthermore, the stochastically appeared imbalanced helicity could be driven to desired handedness by utilizing slight chiral solvents such as (R)- or (S)-terpinen-4-ol. Remarkably, the handedness of supramolecular assemblies thus formed could be kept even when the chiral solvents were removed. For the first time, we show that symmetry breaking can occur in supramolecular gel system driven exclusively through pi-pi stacking.