Azobenzene-Containing Liquid Crystalline Twisted Ribbons via Polymerization-Induced Hierarchical Self-Assembly

Polymerization-induced self-assembly incorporating liquid crystallization, as a polymerization-induced hierarchical self-assembly (PIHSA) method to produce polymeric particles with anisotropic morphologies facilely and efficiently, has drawn wide attention recently. However, the means of regulating the morphologies of liquid crystalline (LC) polymer assemblies still need to be explored. Herein, a route is presented to fabricate the twisted ribbons via PIHSA containing azobenzene based on poor reversible addition-fragmentation chain transfer (RAFT) control, called poorly controlled PIHSA. Cyano-4-(dodecylsulfanylthiocarbonyl)sulfanyl pentanoic acid-2-(2-pyridyldithio) ethyl ester is used as the RAFT agent with poor controllability, and the morphological evolution from ribbons to twisted ribbons can be observed in the corresponding PIHSA system. The formation mechanism of the twisted ribbons is studied systematically and the broad molecular weight distribution is considered to be the decisive factor. Moreover, the supramolecular chirality induced by symmetry breaking is also related to the twist of the ribbons. This study enriches the methods of controlling the morphologies of LC polymer particles and is helpful for further clarifying the mechanism of PIHSA.

Automated summary

Polymerization-induced self-assembly (PIHSA) is a convenient and efficient method to produce polymeric particles with anisotropic morphologies, and it has attracted wide attention. In this study, twisted ribbons were fabricated via PIHSA incorporating azobenzene based on poorly controlled reversible addition-fragmentation chain transfer (RAFT). The formation mechanism of the twisted ribbons and the role of broad molecular weight distribution and supramolecular chirality were systematically studied, enriching the methods of controlling the morphologies of LC polymer particles and providing insights into the mechanism of PIHSA.