An air-stable supported Cu(I) catalyst, CuI@PS-Phen, was designed and synthesized. CuI@PS-Phen can efficiently catalyze the click polymerization of diynes a and diazides b to produce soluble and thermally stable polytriazoles with high molecular weights (M w up to 30800), and low copper residue content (down to 190 ppm) in high yields (up to 94.2%) under mild reaction conditions without the exclusion of oxygen.

Axial chiral aggregation-induced emission (AIE) luminogens of (R)-3,3′-BTPE-BINA, (R)-6,6′-BTPE-BINA and (S)-6,6′-BTPE-BINA were synthesized for the first time by covalently attaching the AIE-active tetraphenylethene (TPE) units to the axial chiral binaphthol (BINOL) moieties at their 3,3′- or 6,6′-positions. It was found that the circular dichroism (CD) value when TPE was attached to BINOL at its 3,3′-positions was much larger than that found after its attachment at 6,6′-positions. The resultant AIE-active luminogens (AIEgens) show high quantum yields (up to 42.4%) in their aggregated states. Interestingly, these AIEgens exhibit an abnormal aggregation-annihilation CD (AACD) phenomenon. The decrease in the twisted angle between the two naphthalene rings upon aggregation was rationalized as the cause of this unique effect.

Aromatic alkynes and azides were successfully polymerized under metal-free conditions using tetramethylammonium hydroxide (NMe4OH) as an organocatalyst at room temperature and soluble 1,5-regioregular polytriazoles P3a–P3e with high molecular weights (Mw up to 56 000) were readily produced in high yields (up to 96%).

The Cu(I)-catalyzed azide-alkyne click polymerization is well developed and broadly applied to the preparation of functional polymers. The removal of copper residues from the resultant polymers is, however, difficult. One way to completely circumvent this difficulty is to develop click polymerization without the use of metallic catalysts, i.e., metal-free click polymerization (MFCP). Herein, recent efforts towards developing MFCP of activated alkynes and azides, and of activated azides and alkynes, to produce regioregular polytriazoles are summarized, and the properties and applications of the resultant polymers are also briefly discussed.

The “thio-click” polymerization is a well-expanded concept of click polymerization. Among the click polymerizations, the thiol–yne click polymerization is less developed and still in its infancy stage. In general, UV light, elevated temperature, amine, or transition metal complexes is needed to catalyze the thiol–yne click polymerization, which greatly complicates the experimental operation and limits its application. In this work, a facile and powerful thiol–yne click polymerization was developed, which could be carried out under very mild conditions without using external catalyst. Simply mixing the aromatic diynes (1a–1e) and dithiols (2–4) with equivalent molar ratio in THF at 30 °C will readily produce soluble and regioregular functional poly(vinylene sulfide)s (PIa–PIe, PII, and PIII) with high molecular weights (Mw up to 85 200) in excellent yields (up to 97%) after as short as 2 h. Furthermore, no double addition product of an ethynyl group was found. This catalyst-free thiol–yne click polymerization has remarkably simplified the reaction conditions and will facilitate the preparation of functional materials applied in diverse areas.