Metal‐Free Click Polymerization: Synthesis and Photonic Properties of Poly(aroyltriazole)s

Abstract Regioselective 1,3‐dipolar polycycloadditions of tetraphenylethene (TPE)‐containing diazides 1 – 3 and bis(aroylacetylene) 4 are initiated by simple heating, affording poly(aroyltriazole)s (PATAs) P I –P III with high molecular weights in high yields. The PATAs are completely soluble in common organic solvents and stable at temperatures up to 358 °C. Thanks to their TPE units, the polymers show aggregation‐induced emission and work as explosive sensors with high sensitivity. The PATAs are optically transparent in the whole visible spectral region. Their refractive indexes can be tuned to a great extent (Δ n ≈ 0.08) by simply changing their alkyl spacer lengths. The modified Abbé numbers of the PATAs are very high (up to 273), indicative of very low optical dispersions in the telecommunication‐important wavelength region. UV irradiation through a photomask quenches the light emissions of the polymers, enabling the generation of two‐dimensional fluorescent images without development. The polymers can be readily photo‐crosslinked, yielding three‐dimensional patterns with high resolutions.