A Dithio Vinylthio C ₂ Synthon Enabling Crystalline and Luminescent Sulfur‐Decorated Polymers

While thioether linkages are commonly associated with soft and amorphous polymer backbones, herein, we show that a calcium carbide-derived α,ω-bis(vinylthio) synthon enables crystalline, sequence-defined sulfur polymers with nonconventional luminescence. A single-step thiol-yne addition reaction uses acetylene generated in situ from industrial calcium carbide (CaC₂) to produce a modular C₂ vinyl sulfide (also known as vinylthio) monomer that undergoes quantitative, light-induced thiol-ene step-growth polymerization with aliphatic dithiols. Type I photoinitiation ensures complete anti-Markovnikov addition to give C₂ -segmented poly(thioether)s, while thermal and base-mediated conditions generate hybrid poly(thioether)/polydisulfide structures. The resulting sulfur-rich backbones display sharp melting transitions, spherulitic crystallization, one-step thermal decomposition up to about 316°C, and pronounced cluster-triggered emission arising from dense thioether clustering and through-space conjugation. Green metric analysis reveals high Atom Economy and essentially waste-free polymer formation, thereby linking efficient use of an established C₂ synthon to precision sulfur polymer design. This C₂ vinylthio platform provides a general strategy to convert classically soft thioether motifs into structurally ordered and luminescent materials, and establishes vinyl sulfides as powerful, yet underutilized, building blocks in sustainable polymer chemistry.