Synthesis and photophysical properties of porphyrin-containing polymers

A series of porphyrin-containing polymers with triazole rings as linkers have been successfully synthesized by click polymerization. The polycycloadditions of porphyrin-containing dialkyne 1 and 1,4-diazidobenzene 2 were initiated either by simple heating or by Cu(I)-catalyst, affording polymers P1-P8 with relatively high molecular weight. The polymerization process was monitored by gel permeation chromatography analysis. The polymer prepared by thermally initiated click polymerization has unimodal molecular weight distribution and moderate polydispersity index after prolonging reaction time to 170 h. Compared with the metal-free click polymerization, the rate of molecular weight growth in Cu(I)-catalyzed click polymerization declined, leading to relatively low molecular weight of the resulting polymer. The as-synthesized polymers are soluble in common organic solvents and stable at a temperature up to 350 °C. The photophysical properties of the porphyrin monomer and the polymer were investigated by UV–vis and fluorescence spectroscopy. This approach offers practical advantages over other synthetic methods used to prepare main-chain porphyrin-containing polymers with regard to the absence of byproducts generated during the polymerization reaction.