Understanding the microphase separation of charged block copolymers (BCPs) is very important for the development of functional materials with tunable structures. Although the morphological behavior of charged BCPs in bulk and in solution has been explored, the three-dimensional (3D) confined self-assembly of charged BCPs is still unknown. Here, we report the confined assembly of positively charged polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) in emulsion droplets. The fraction of charged segments can be well tailored by the quaternization of the 4VP unit with methyl iodide. A series of BCP particles, including pupa-like, onion-like, bumpy, sphere-in-sphere particles, large compound vesicles, and others, could be obtained by tuning the charge fraction and block ratio of BCPs. The introduction of charge affected the hydrophilicity and chain conformation of BCPs, leading to the change in the morphology of assemblies. Moreover, the addition of inorganic salts showed an obvious effect on the assembly of charged PS-b-P4VP, whose morphology was dependent on the hydration nature of the counterions. This work not only presents a fundamental understanding of the self-assembly of charged BCP under 3D confinement but also inspires the design and preparation of functional nanoparticles with tunable morphologies.

Halogen‐bond driven assembly, a world parallel to hydrogen‐bond, has emerged as an attractive tool for constructing (macro)molecular arrangement. However, knowledge about halogen‐bond mediated confined‐assembly in emulsion droplets is limited so far. An I….N bond mediated confined‐assembly pathway to enable order‐order phase transitions is reported here. Compared to hydrogen bonds, the distinct features of halogen bonds (e.g., higher directionality, hydrophobicity, favored in polar solvents), offers opportunities to achieve novel nanostructures and materials. Polystyrene‐b‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) AB diblock copolymer is chosen as halogen acceptor, while an iodotetrafluorophenoxy substituted C‐type homopolymer, (poly(3‐(2,3,5,6‐tetrafluoro‐4‐iodophenoxy)propyl acrylate), PTFIPA) is designed as halogen donor, synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization. Formation of halogen bonding donor–acceptor pairs between the PTFIPA homopolymer and the P4VP segments presented in PS‐b‐P4VP, increase the volume of P4VP domains, in turn inducing an order‐to‐order morphology transition sequence: changing from spherical → cylindrical → lamellar → inverse cylindrical, by tuning the PTFIPA content and choice of surfactant. Subsequent selective swelling/deswelling of the P4VP domains give rise to further internal morphology transitions, creating tailored mesoporous microparticles, disassembled nanodiscs, and superaggregates. It is believed that these results will stimulate further examinations of halogen bonding interactions in emulsion droplets and many areas of application.

A library of nanostructures and multi-stage morphology transformation are realized by introducing a 3D confined assembly to hydrogen-bonded comb-shaped supramolecular polymer architectures.

A straightforward synthesis of α-Ba, ω-TAP functionalized polymers, Ba-PnBuA-TAP, is reported, leading to the formation of double-crosslinked supramolecular networks driven via the sequential hydrogen-bonding association and metal-coordination.