Programmable Reconfiguration of Supramolecular Bottlebrush Block Copolymers: From Solution Self‐Assembly to Co‐Crystallization‐Assistant Self‐Assembly

Abstract

Achieving structural reconfiguration of supramolecular bottlebrush block copolymers toward topological engineering is of particular interest but challenging. Here, we address the creation of supramolecular architectures to discover how assembled topology influences the structured aggregates, combining hydrogen‐bonded (H‐bonded) bottlebrush block copolymers and electrostatic interaction induced polymer/inorganic eutectics. We first design H‐bonding linear‐brush block copolymer P(NBDAP‐co‐NBC)‐b‐P(NBPEO), bearing linear block P(NBDAP‐co‐NBC) (poly(norbornene‐terminated diaminopyridine‐co‐norbornene‐terminated hexane)) with pendant H‐bonding DAP (diaminopyridine) motifs, and PEO (poly(ethylene oxide)) densely grafted P(NBPEO) brush block. Thanks to H‐bonding association between DAP and thymine (Thy), incorporation of Thy‐functionalized polystyrene (Thy‐PS) enables solution self‐assembly and formation of H‐bonded bottlebrush block copolymers, generating augmented nanospheres with increasing Thy‐PS amount. Noteworthy that integration of inorganic cluster silicotungstic acid (STA) to P(NBC‐co‐NBDAP)‐b‐P(NBPEO), endows the formation of PEO/STA eutectic core. Therefore, co‐crystallization‐assistant self‐assembly at the interfaces of polymeric, inorganic and supramolecular chemistry is realized, reflecting multi‐stage morphology transformation from hexagonal platelets, needle‐like, curved rod‐like micelles, finally to end‐to‐end closed rings, by gradually increasing Thy‐PS while fixing STA content. Interestingly, such solution self‐assembly to co‐crystallization‐assistant self‐assembly strategy not only endows unique nanostructure transition, also induce in‐to‐out switch of PS domains. These findings clearly provide unique methodology towards programmable fabrication of geometrical objects promising in smart materials.