Pyridine-Diketopyrrolopyrrole-Based Novel Metal-Free Visible-Light Organophotoredox Catalyst for Atom-Transfer Radical Polymerization
Long Yang, Yujie Huang, Yuting Peng, Fei Liu, Qingchun Zhang, Huichao He, Jun Wang, Long Jiang, Yong Zhou
Abstract
In the field of electronics, organocatalysts are in high demand for use in the synthesis of clean polymers using solar radiation rather than potentially contaminating metals. Combining theoretical design, simulation, and experiments, this work presents a novel, pyridine-diketopyrrolopyrrole (P-DPP)-based metal-free visible-light organophotoredox catalyst (P-DPP). It is effective in the photocontrolled organocatalytic atom-transfer radical polymerization (O-ATRP) of methyl methacrylate (MMA) and styrene. The use of this catalyst and white light-emitting diode (LED) irradiation produces polymers with a cross-linked feature. In O-ATRP, the P-DPP catalyst has an oxidative quenching catalytic mechanism with an excited-state reductive potential of −1.8 V, fluorescence lifetime of 7.5 ns, and radical-cation oxidative potential of 0.45 V. Through molecular simulation, we found that the adjacent pyridine group is key to reducing the alkyl halide initiator and generating radicals, while the diketopyrrolopyrrole core stabilizes the triplet state of the catalyst through intramolecular charge transfer. The findings related to this novel photoredox catalyst will aid in the search for much more effective organophotoredox catalysts for use in controlled radical polymerization. They will also be of value in the fields of polymer chemistry and physics and in various applications.