Balancing Chain Mobility and Liquid-Crystalline Order in Block Copolymers Enables Fusion–Rearrangement-Driven Hierarchical Assemblies

Liquid-crystalline block copolymers (LC-BCPs) typically form structurally precise one-dimensional assemblies via nucleation–epitaxial growth, whereas constructing hierarchical structures generally relies on fusion–rearrangement processes. However, effectively balancing polymer chain mobility and LC order to direct such fusion–rearrangement pathways remains challenging, particularly when targeting multicomponent hierarchical heterostructures. Here, we synthesized a series of poly(cyclopropane-1,1-dicarboxylate)-based BCPs (PEG45-b-P(m)Choln) featuring asymmetric dicarboxylate pendent groups that enhance chain mobility while maintaining LC order. These BCPs self-assembled into bamboo-like hierarchical micelles through a fusion–rearrangement pathway characterized by perpendicular lamellar LC domains and multilayered surface structures. Upon coassembly with an amino acid-derived chiral amphiphile bearing a homologous mesogen, the micelles undergo a similar pathway, during which molecular chirality is transferred and amplified, ultimately evolving into well-defined superhelical fibers. This work highlights the cooperative roles of LC ordering and fusion–rearrangement and provides a versatile strategy for constructing hierarchical and biomimetic architectures from LC-BCPs.