Photoinduced organocatalyzed atom transfer radical polymerization (O-ATRP) is a controlled radical polymerization methodology catalyzed by organic photoredox catalysts (PCs). In an efficient O-ATRP system, good control over molecular weight with an initiator efficiency (I* = M n,theo /M n,exp × 100%) near unity is achieved, and the synthesized polymers possess a low dispersity (Đ). N,N-Diaryl dihydrophenazine catalysts typically produce polymers with low dispersity (Đ < 1.3) but with less than unity molecular weight control (I* ∼ 60−80%). This work explores the termination reactions that lead to decreased control over polymer molecular weight and identifies a reaction leading to radical addition to the phenazine core. This reaction can occur with radicals generated through reduction of the ATRP initiator or the polymer chain end. In addition to causing a decrease in I*, this reactivity modifies the properties of the PC, ultimately impacting polymerization control in O-ATRP. With this insight in mind, a new family of core-substituted N,N-diaryl dihydrophenazines is synthesized from commercially available ATRP initiators and employed in O-ATRP. These new core-substituted PCs improve both I* and Đ in the O-ATRP of MMA, while minimizing undesired side reactions during the polymerization. Further, the ability of one core-substituted PC to operate at low catalyst loadings is demonstrated, with minimal loss of polymerization control down to 100 ppm (weight average molecular weight [M w ] = 10.8 kDa, Đ = 1.17, I* = 104% vs M w = 8.26, Đ = 1.10, I* = 107% at 1000 ppm) and signs of a controlled polymerization down to 10 ppm of the catalyst (M w = 12.1 kDa, Đ = 1.36, I* = 107%).

Organocatalyzed atom transfer radical polymerization (O-ATRP) is a method of producing polymers with precise structures under mild conditions using organic photoredox catalysts (PCs). Due to the unknown toxicity of PCs and their propensity to introduce color in polymers synthesized by this method, removal of the PC from the polymer product can be important for certain applications of polymers produced using O-ATRP. Current purification methods largely rely on precipitation to remove the PC from the polymer, but a more effective and efficient purification method is needed. In this work, an alternative purification method relying on oxidation of the PC to PC Á+ followed by filtration through a plug to remove PC Á+ from the polymer and removal of the volatiles was developed. A range of chemical oxidants and stationary phases were tested for their ability to remove PCs from polymers, revealing chemical oxidation by N-bromosuccinimide followed by a filtration through a silica plug can remove up to 99% of the PC from poly(methyl methacrylate).Characterization of the polymer before and after purification demonstrated that polymer molecular weight, dispersity, and chain-end fidelity are not signficantly impacted by this purification method. Finally, this purification method was tested on a range of dihydrophenazine, phenoxazine, dihydroacridines, and phenothiazine PCs, revealing the strength of the chemical oxidant must match the oxidation potential of the PC for effective purification.