Hierarchical Self-Organization and Uniaxial Alignment of Well Synthesized Side-Chain Discotic Liquid Crystalline Polymers

Liquid crystalline polymers (LCPs) combine the attributes of liquid crystals and polymers, while discotic LCPs have been less developed in sharp contrast to their calamitic counterparts mainly due to lack of suitable discotic LCP materials. Here we successfully prepared a series of well-defined triphenylene (TP) based discotic LC polyacrylates via reversible addition–fragmentation chain-transfer (RAFT) polymerization for the first time, and through a combination of multiple analysis techniques and phase transition kinetics study, a remarkable molecular weight effect or polymer effect at a critical degree of polymerization (DP) around 20 has been disclosed. Moreover, the first proposed discrete columnar stacks (DCS) based hierarchical self-organization model accounts well for the formation and transformation of ordered hexagonal columnar lattice Col_ho dominated by side-chain TP stacking and oblique columnar superlattice Col_ob‑s induced by compaction and ordering of polymer backbones. The in-depth understanding of their superstructures and readily achieved uniaxial alignment pave the way for the rational design and preparation of such kind of solution processable cutting-edge polymeric semiconducting materials and may boost various fascinating optoelectronic applications