Photocatalytic ATRP Depolymerization: Temporal Control at Low ppm of Catalyst Concentration.

A photocatalytic ATRP depolymerization is introduced that significantly suppresses the reaction temperature from 170 to 100 °C while enabling temporal regulation. In the presence of low-toxicity iron-based catalysts and under visible light irradiation, near-quantitative monomer recovery could be achieved (up to 90%), albeit with minimal temporal control. By employing ppm concentrations of either FeCl 2 or FeCl 3 , the depolymerization during the dark periods could be completely eliminated, thus enabling temporal control and the possibility to modulate the rate by simply turning the light "on" and "off". Notably, our approach allowed preservation of the end-group fidelity throughout the reaction, could be carried out at high polymer loadings (up to 2M), and was compatible with various polymers and light sources. This methodology provides a facile, environmentally friendly, and temporally regulated route to chemically recycle ATRP-synthesized polymers, thus opening the door for further opportunities.