Sequentially Hetero-functional, Topological Polymers by Step-growth Thiol-yne Approach

Sequence-controlled polymers (SCPs) such as DNA and proteins play an important role in biology. Many efforts have been devoted to synthesize SCPs in the past half a century. However, to our knowledge, the artificial sequences containing independently functional groups have never been reported. Here, we present a facile and scalable approach based on radical-initiated step-growth polymerization to synthesize sequence-controlled functional polymers (SCFPs) with various topologies, covering from linear to random and hyperbranched polymers. The functional groups, such as OH/NH2, OH/COOH, and NH2/N3, alternately arranged along the chain, which were further selectively functionalized to achieve DNA-mimic and hetero-multifunctional SCPs. This user-friendly strategy exhibits advantages of commercially available monomers, catalyst-free process, fast reaction, high yield and water solvent, opening a general approach to facile and scalable synthesis of SCFPs.