Construction of Functional Hyperbranched Poly(phenyltriazolylcarboxylate)s by Metal‐Free Phenylpropiolate‐Azide Polycycloaddition

The 1,3-dipolar cycloaddition of activated internal alkynes with azides has been developed into an efficient polymerization reaction for constructing functional linear 1,4,5-trisubstitued polytriazoles. However, it is rarely employed for the synthesis of hyperbranched polymers. In this work, metal-free polycycloadditions of tris(3-phenylpropiolate)s (1) and tetraphenylethene-containing diazides (2) are performed in dimethylformamide at 100 °C for 7 and 12 h, producing hyperbranched poly(phenyltriazolylcarboxylate)s (hb-PPTCs) with high molecular weights and satisfactory regioregularities in good yields. The hb-PPTCs have good solubility in common organic solvents and high thermal stability. They are non-emissive in solutions, but emit intensively upon aggregation, showing an aggregation-induced emission effect. Their aggregates can work as fluorescent sensors for explosive detection with high sensitivity. Furthermore, the polymers can be utilized for the fabrication of 2D fluorescent patterns with high resolution by UV irradiation through copper grid masks.