Molecular Photothermal Conversion Catalyst Promotes Photocontrolled Atom Transfer Radical Polymerization.

Photothermal conversion is a growing research area that promotes thermal transformations with visible light irradiation. However, few examples of dual photothermal conversion and catalysis limit the power of this phenomenon. Here, we take inspiration from nature's ability to use porphyrinic compounds for nonradiative relaxation to convert light into heat to facilitate thermal polymerization catalysis. We identify the photothermal conversion catalytic activity of a vitamin B 12 derivative, heptamethyl ester cobyrinate (HME-Cob), to perform atom transfer radical polymerization (ATRP) under irradiation. Rapid polymerization are obtained under photothermal activation while maintaining good control over polymerization with the aid of a photoinitiator to enable light-induced catalyst regeneration. The catalyst exhibits exquisite temporal control in photocontrolled thermal polymerization. Ultimately, the activation of this complex is accessed across a broad range of wavelengths, including near-IR light, with excellent temporal control. This work showcases the potential of developing photothermal conversion catalysts.