Theory of Polygonal Phases Self-Assembled from T‑Shaped Liquid Crystalline Molecules

Extensive experimental studies have shown that numerous ordered phases can be formed via the self-assembly of T-shaped liquid crystalline molecules (TLCMs) composed of a rigid backbone, two flexible end chains, and a flexible side chain. However, a comprehensive understanding of the stability and formation mechanisms of these intricately nanostructured phases remains incomplete. Here, we fill this gap by carrying out a theoretical study of the phase behavior of TLCMs. Specifically, we construct phase diagrams of TLCMs by computing the free energy of different ordered phases of the system. Our results reveal that the number of polygonal edges increases as the length of the side chain or interaction strength increases, consistent with experimental observations. The theoretical study not only reproduces the experimentally observed phases and phase transition sequences but also systematically analyzes the stability mechanism of the polygonal phases.