Design, Scalable Synthesis, and Characterization of Poly(Oligourethane Methacrylate)s Bottlebrushes with Discrete, Sequence-Defined, and Stereocontrolled Side-Chains.

Sequence and stereocontrol govern the sophisticated functionalities of biopolymers, such as proteins and nucleic acids. Unfortunately, although conventional polymerization methods are easy to perform, they often yield polymers with broad structural distributions, which limits the precise control over their physical properties and functions. To bridge this gap, we present a strategy for fabricating poly-(oligourethane methacrylate)-s with sequence-defined, stereospecific pendant chains via radical polymerization. These materials represent a new class of precision-engineered bottlebrush polymers in which each side chain carries encoded structural information. The use of scalable, solution-phase multistep synthesis in a one-pot method enables the efficient production of oligourethane macromonomers with tunable sequence and stereochemistry, derived from commercially available chiral amino alcohols. When tethered to a polymeric backbone, these precisely structured side chains impart programmable properties, including thermal and chiroptical characteristics. This approach enables the transfer of molecular-level information encoded in side chains into macroscopic material properties, opening new avenues for the design of advanced functional polymers. Our findings lay the foundation for developing bottlebrush polymers as adaptable materials with tailored conformations, self-folding behavior, and potential bioinspired activity, pushing the boundaries of synthetic polymer design toward the complexity of biological systems.