Self-Assembly of Polymer Nanostructures through Halogen Bonding Interactions of an lodoperfluoroarene-Functionalized Polystyrene Derivative

A structurally novel iodoperfluoroarene-substituted polystyrene has been synthesized, and its noncovalent halogen bonding interactions with polymeric Lewis bases have been studied. RAFT polymerization was used to generate halogen bond donating polystyrene derivatives: with low dispersities. Coassembly of the halogen bond donor polymer with an amine-functionalized methacrylate block copolymer was achieved using a solvent switching protocol and studied by electron microscopy and dynamic light scattering analysis. The structures obtained include spheres, wormlike structures, and vesicles as well as inverted morphologies such as hexagonally packed hoops and bicontinuous structures, which have been challenging to access by conventional assembly methods. The ability to access such inverted structures suggests that complexes generated by noncovalent interactions between complementary macromolecules can display high effective packing parameters, giving rise to behavior that has generally required unconventional macromolecular architectures (e.g., dendrimers, branched, or triblock copolymers). The effects of polymer composition, assembly conditions, and the presence of halogen bond donating small molecules on the outcome of the assembly are discussed, along with NMR and X-ray photoelectron spectroscopy studies of the interpolymer halogen bonding interactions in this system.