Transition metal-free thiol–yne click polymerization toward Z-stereoregular poly(vinylene sulfide)s

Click polymerization has emerged as a versatile polymerization technique for the construction of functional polymers. In this work, a novel transition metal-free thiol–yne click polymerization with high regio- and stereoselectivities was successfully developed. The polymerizations were conducted in the presence of K3PO4, and sole anti-Markovnikov adducts of poly(vinylene sulfide)s (PVSs) with high molecular weights and high stereoregularity (Z-isomer contents up to 100%) were obtained in high yields after 24 h. The resultant PVSs are thermally stable and show high refractive indices owing to the high contents of aromatic rings and sulfur atoms in the structures. Moreover, PVSs with aggregation-induced emission (AIE) characteristics could also be produced by introducing AIE-active tetraphenylethene (TPE) moieties into the polymer chains. This K3PO4-mediated thiol–yne click polymerization with high efficiency and great robustness has great potential in the preparation of functional PVSs.