The development of new polymerization reactions is of critical importance to macromolecule science. In this critical review, we summarize the research efforts to incubate alkyne-azide click reactions into a versatile polymerization technique for the synthesis of poly(triazole)s (PTAs) with linear and hyperbranched structures. Cu(I)- and Ru(II)-catalyzed click polymerizations afforded 1,4- and 1,5-regioregular PTAs, respectively. Whereas traditional thermal cycloadditions normally generate regiorandom products, PTAs with 1,4-regioisomer contents up to 95% were created by utilizing the electronic effect involved in the thermal click polymerizations of aroylacetylenes with azides. The PTAs showed unique functional properties, such as luminescence, chromism, fluorescence imaging, emission superquenching, chain helicity, optical nonlinearity, light refractivity, photovoltaic effect, cytocompatibility and biodegradability (145 references).
