Metalloporphyrin-bound Janus nanocomposites with dual stimuli responsiveness for nanocatalysis in living radical polymerization

Abstract

The capability to spatiotemporally regulate polymerization kinetics in response to dual external stimuli of light and magnetism offers exciting pathways to precisely manipulate polymer composition and sequence. Herein, we report a strategy that adopts snowman-shaped Fe₃O₄@aSiO₂-click-ZnPTPP Janus nanocomposites with a high magnetization value (12.9 emu g⁻¹) and stably confined but accessible catalytic metalloporphyrin moieties as the nanocatalysts for photo-induced electron transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. This method enables the synthesis of diverse polymeric structures from a large range of monomers using ultralow concentrations of nanocatalysts (less than 10 ppm) with simple modulation of light and magnetism. In addition, the nanocatalysts are found to be oxygen-tolerant, and they exhibit non-agglomeration during polymerization. Finally, repeated regeneration of the used nanocatalysts by magnetic extraction or facile centrifugation effectively reduces or even eliminates the contamination and/or decomposition on the final polymer products.