Symmetry Breaking in Supramolecular Gel Condensation

Abstract

Supramolecular condensation during cooling cycles often transitions through multiple metastable phases before achieving a stable crystalline state. Metastability arises from various competing parameters like symmetrical arrangement, and supramolecular bonding and manifests at different temperatures. Symmetrical physical arrangements can minimize vibrational energy and stabilize the systems at higher temperatures. Further cooling promotes directional supramolecular bonding, such as charge‐assisted hydrogen bonding, resulting in molecular periodicity within metastable structures. Frustration occurs when weaker van der Waals bonds form during further cooling, propagating perpendicularly to stronger one‐dimensional charge‐assisted hydrogen bonds and disrupting lateral periodicity in certain solvents. This makes parallel 1D fibers slidable, adding flexibility to the gel fiber. Eventually, some supramolecular systems attain thermodynamically stable crystalline states by perfectly arranging all the molecules. Throughout the process, metastability results from different symmetrical arrangements, and each rearrangement alters the supramolecular structure‘s symmetry, generating new physicochemical properties. Different supramolecular gels uniquely break symmetry, which can be monitored through various techniques. This perspective analyzes supramolecular thermoreversible, reverse thermal, liquid crystalline, thixotropic, and antisolvent‐induced gels to illustrate spontaneous symmetry reduction processes. Reaching a suprasymmetry condensate can classify big data and be applied in unconventional analogue computing or data storage.