Phase Behaviour of X-Shaped Liquid Crystalline Molecules

TL;DR

This study uses self-consistent field theory to explore the phase behavior of X-shaped liquid crystalline molecules, revealing diverse ordered structures and phase transitions influenced by side chain symmetry and length.

Contribution

It provides a comprehensive theoretical analysis of phase diagrams and structural transitions in XLCMs, including predictions consistent with experiments and insights into stabilization mechanisms.

Findings

Multiple stable ordered phases including smectic-A, triangle-square, pentagon, and giant polygon.

Phase transitions between layered and polygonal structures driven by side chain asymmetry.

Theoretical phase diagrams align with experimental observations for symmetric side blocks.

Abstract

X-shaped liquid crystalline molecules (XLCMs) are obtained by tethering two flexible end A-blocks and two flexible side B-blocks to a rigid backbone (R). A rich array of ordered structures can be formed from XLCMs, driven by the competition between the interactions between the chemically distinct blocks and the molecular connectivity. Here, we report a theoretical study on the phase behaviour of XLCMs with symmetric and asymmetric side blocks by using the self-consistent field theory (SCFT). A large number of ordered structures, including stable smectic-A, triangle-square, pentagon and giant polygon, are obtained as solutions of the SCFT equations. Phase diagrams of XLCMs as a function of the total length and asymmetric ratio of the side chains are constructed. For XLCMs with symmetric side blocks, the theoretically predicted phase transition sequence is in good agreement with experiments. For XLCMs with a fixed total side chain length, transitions between layered structure to polygonal phases, as well as between different polygonal phases, could be induced by varying the asymmetry of the side chains. The free energy density, domain size, side-chain stretching , and molecular orientation are analyzed to elucidate mechanisms stabilizing the different ordered phases.