From a Single Synthon Monomer to Diverse Macromolecules: Propargylate-Based Diversity-Oriented Polymerization

Diversity-oriented polymerization (DOP), which transforms a single monomer precursor into structurally distinct polymers via controlled divergent pathways, represents a powerful strategy for rapidly accessing a wide range of functional polymers. However, developing feasible and broadly applicable DOP methods using a single synthon monomer remains a long-standing challenge in polymer chemistry. Herein, we report a DOP strategy based on propargylate monomers, whose divergent reactivity can be precisely regulated under mild conditions to synthesize five distinct polymer classes: polytriazoles, E -polyacrylamides, Z -polyacrylamides, E -polyacrylamide- alt -polytriazoles, and Z -polyacrylamide- alt -polytriazoles. This DOP strategy features broad monomer scope and excellent stereoselectivity (exclusively E- or Z -configuration), establishing a versatile platform for the on-demand synthesis of polymers with programmable sequences and stereochemistry, and offering new opportunities for diversity-driven materials discovery.