Convoluted Micellar Morphological Transitions Driven by Tailorable Mesogenic Ordering Effect from Discotic Mesogen-Containing Block Copolymer

Abstract

Abstract Solution-state self-assemblies of block copolymers (BCPs) to form nanostructures are tremendously attractive for their tailorable morphologies and functionalities. While incorporating moieties with strong ordering effects may introduce highly orientational control over the molecular packing and dictate assembly behaviors, subtle and delicate driving forces can yield slower kinetics to reveal manifold metastable morphologies. Herein, we reported the unusually convoluted self-assembly behaviors of a liquid crystalline (LC) BCP bearing triphenylene discotic mesogens. They underwent unprecedented multiple morphological transitions spontaneously, driven by their intrinsic subtle LC ordering effect. Meanwhile, LC orderedness could also be instantly built by doping the mesogens with small-molecule dopants, and the morphological transitions were dramatically accelerated and various exotic micelles were produced. Surprisingly, with high doping levels, the self-assembly mechanism of this BCP was completely changed from intramicellar chain shuffling and rearrangement to nucleation-growth mode, based on which self-seeding experiments could be conducted to produce highly uniform fibrils.