Near-Infrared Light and Acid/Base Dual-Regulated Polymerization Utilizing Imidazole-Anion-Fused Perylene Diimides as Photocatalysts

This work presents the first example of acid/base-responsive and near-infrared (NIR)-absorbing photocatalysts based on imidazole-anion-fused perylene diimide chromophores. The photocatalysts were in situ generated by deprotonation of imidazole-fused perylene diimide under an alkaline environment. NIR (λ = 730 nm, 128 mW/cm²) photoinduced atom transfer radical polymerization (ATRP) was implemented, exhibiting high efficiency and excellent livingness under ppm level of photocatalysts (15 ppm relative to monomer) and Cu(II) complex (10 ppm relative to monomer) concentrations. The method showed capabilities to polymerize behind opaque barriers (i.e., paper and pig skin) and under aerobic condition. Notably, this work demonstrated a dual temporal control of polymerization by adding weak base/acid and switching NIR light on/off. The polymerization can even be halted by bubbling CO₂ and was then fully recovered by adding triethylamine. The NIR photoATRP of acrylamide monomers in aqueous solution was also performed, which can be regulated by the change of pH.