Tunable Phase Structure of Side-chain Liquid Crystalline Polymers Enabled by Molecular Engineering of Dual Mesogenic Cores

A series of novel side-chain liquid crystalline (SCLC) copolymers were synthesized by attaching two distinct mesogenic units, namely a chiral cholesteryl-based monomer (M1) and an achiral biphenyl-based monomer (M2), to a poly(3-mercaptopropylmethylsiloxane) (PMMS) backbone via thiol-ene click chemistry. The influence of side chain composition on the self-assembly behavior and phase structures of these SCLC copolymers was systematically investigated using different instrument. Results indicate that three distinct liquid crystalline phases and four unique molecular configurations were identified within the polymer series, with the emergence of the liquid crystalline phase being a synergistic outcome of the two distinct side chains. This study underscores the critical influence of side chain dimensions, rigidity, and spatial volume on the self-assembly structures and phase characteristics of liquid crystalline polymers, providing valuable insights for the rational design and development of advanced functional materials with tailored properties.