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Organocatalyzed atom transfer radical polymerization (O-ATRP) is a controlled radical polymerization method mediated by organic photoredox catalysts (PCs) for producing polymers with well-defined structures. While N,N-diaryl dihydrophenazine PCs have successfully produced polymers with low dispersity (Đ < 1.3) in O-ATRP, low initiator efficiencies (I* ∼ 60–80%) indicate an inability to achieve targeted molecular weights and have been attributed to the addition of radicals to the PC core. In this work, we measure the rates of alkyl core substitution (AkCS) to gain insight into why PCs differing in N-aryl group connectivity exhibit differences in polymerization control. Additionally, we evaluate how PC properties evolve during O-ATRP when a non-core-substituted PC is used. PC 1 with 1-naphthyl groups in the N-aryl position resulted in faster AkCS (k1 = 1.21 ± 0.16 × 10–3 s–1, k2 = 2.04 ± 0.11 × 10–3 s–1) and better polymerization control at early reaction times as indicated by plots of molecular weight (number average molecular weight = Mn) vs conversion compared to PC 2 with 2-naphthyl groups (k1 = 6.28 ± 0.38 × 10–4 s–1, k2 = 1.15 ± 0.07 × 10–3 s–1). The differences in rates indicate that N-aryl connectivity can influence polymerization control by changing the rate of AkCS PC formation. The rate of AkCS increased from the initial to the second substitution, suggesting that PC properties are modified by AkCS. Increased PC radical cation (PC•+) oxidation potentials (E1/2 = 0.26–0.27 V vs SCE) or longer triplet excited-state lifetimes (τT1 = 1.4–33 μs) for AkCS PCs 1b and 2b compared to parent PCs 1 and 2 (E1/2 = 0.21–0.22 V vs SCE, τT1 = 0.61–3.3 μs) were observed and may explain changes to PC performance with AkCS. Insight from evaluation of the formation, properties, and performance of AkCS PCs will facilitate their use in O-ATRP and in other PC-driven organic transformations. 

Photoinduced organocatalyzed atom-transfer radical polymerization (O-ATRP) is a controlled radical polymerization technique that can be driven using low-energy, visible light and makes use of organic photocatalysts. Limitations of O-ATRP have traditionally included the need for high catalyst loadings (1000 ppm) and the narrow scope of monomers that can be controllably polymerized. Recent advances have shown that N , N -diaryl dihydrophenazine (DHP) organic photoredox catalysts (PCs) are capable of controlling O-ATRP at PC loadings as low as 10 ppm, a significant advancement in the field. In this work we synthesized five new DHP PCs and examined their efficacy in controlling O-ATRP at low ppm catalyst loadings. We found that we were able to polymerize methyl methacrylate at PC loadings as low as 10 ppm (relative to monomer) while producing polymers with dispersities as low as Đ = 1.33 and achieving initiator efficiencies ( I* ) near unity (102%). In addition to applying these PCs in O-ATRP, we carried out a thorough investigation into the structure–property relationships of the new DHP PCs reported herein and report new photophysical characterization data for previously reported DHPs. The insight into the DHP structure–property relationships that we discuss herein will aid in the elucidation of their ability to catalyze O-ATRP at low catalyst loadings. Additionally, this work sheds light on how structural modifications affect certain PC properties with the goal of bolstering our understanding of how to tune PC structures to overcome current limitations in O-ATRP such as the controlled polymerization of challenging monomers.