Synergistically Stabilized Selenols Enable Click Polymerization Toward Diverse Polymers

The high oxidative sensitivity of selenols has severely prevented their isolation and direct utility as monomers for polymerization. In this work, we design an isolable diselenol monomer with a unique β-oxygenated structure (βO-diselenol), which is stabilized by intramolecular Se–H···O hydrogen bonds and Se···Se chalcogen bonds. This diselenol exhibits over 5-fold higher stability than conventional selenols, enabling the isolation and purification in air. The versatility of βO-diselenols as platform chemicals is showcased by the successful click polymerization with isocyanate, epoxy, alkyne, haloalkane, and alkene monomers, yielding a diverse library of functional polymers. Specifically, catalyst-free click polyaddition with diisocyanates affords a new type of selenium-containing dynamic polymer, polyselenourethanes (PSeUs), featuring high transparency, high refractive indices ( n D = 1.55∼1.62), and adjustable mechanical properties (σ b, 0.35∼28 MPa; ε b, 77.2∼1738.6%). This work innovates a novel selenium-containing polymer synthesis platform based on a stable diselenol monomer, establishing a bridge between organoselenium chemistry and polymer science, unlocking new opportunities for selenium-containing polymers.