Synthesis of Low‐Dimensional Polyion Complex Nanomaterials via Polymerization‐Induced Electrostatic Self‐Assembly

Nanostructured polyion complexes (PICs) are appealing in biomaterials applications. Yet, conventional assembly suffers from the weakness in scale‐up and reproducibility. Only a few low‐dimensional PICs are available to date. Herein we report an efficient and scalable strategy to prepare libraries of low‐dimensional PICs. It involves a visible‐light‐mediated RAFT polymerization of ionic monomer in the presence of a polyion of the opposite charge at 5–50 % w/w total solids concentration in water at 25 °C, namely, polymerization‐induced electrostatic self‐assembly (PIESA). A Vesicle, multi‐compartmental vesicle, and large‐area unilamellar nanofilm can be achieved in water. A long nanowire and porous nanofilm can be prepared in methanol/water. An unusual unimolecular polyion complex (uPIC)‐sphere‐branch/network‐film transition is reported. This green chemistry offers a general platform to prepare various low‐dimensional PICs with high reproducibility on a commercially viable scale under eco‐friendly conditions.