Supramolecular coupling of cylindrical micelles following seeded-growth

Macromolecular coupling is a widely used technique for industrial materials, while supramolecular coupling is ubiquitous in biological systems. Although the designed synthesis of one-dimensional self-assembled nanostructures via crystallization-driven self-assembly and liquid-crystallization-driven self-assembly has been realized, end-to-end coupling of cylindrical micelles is rarely reported. Unlike crystallization, liquid-crystallization features fluidity under certain conditions. The cylindrical micelles prepared via liquid-crystallization-driven self-assembly possess less organized liquid crystalline blocks at the two partially open ends, originating the end-to-end coupling to lower the free energy. The interaction strength of solvents with liquid crystalline blocks is a pivotal parameter that can be used to switch on or off the coupling. Theoretical simulation is consistent with experimental work, supporting the mechanism. The supramolecular coupling offers opportunities for designing complex polymeric liquid crystalline nanostructures.