Radical Addition to N,N-Diaryl Dihydrophenazine Photoredox Catalysts and Implications in Photoinduced Organocatalyzed Atom Transfer Radical Polymerization.

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 (D). N,N-Diaryl dihydrophenazine catalysts typically produce polymers with low dispersity (D < 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 D 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, D = 1.17, I* = 104% vs M w = 8.26, D = 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, D = 1.36, I* = 107%).

N,N-Diaryl Dihydrophenazines as Photoredox Catalysts for PET-RAFT and Sequential PET-RAFT/O-ATRP.

N,N-Diaryl dihydrophenazines are employed as organic photoredox catalysts (PCs) for photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. The ability of these PCs to mediate PET-RAFT is heavily dependent on the ability of the PC to access a photoexcited intramolecular charge transfer state. The use of PCs displaying intramolecular charge transfer in the excited state allows for efficient PET-RAFT of a variety of monomers, including vinyl acetate, and in a wide range of solvents. The ability of these PCs to also mediate organocatalyzed atom transfer radical polymerization (O-ATRP) is exploited to perform a sequential PET-RAFT/O-ATRP block copolymerization of PMA-b-PMMA using the same PC for both polymerizations.

Solvent Effects on the Intramolecular Charge Transfer Character of N,N-Diaryl Dihydrophenazine Catalysts for Organocatalyzed Atom Transfer Radical Polymerization.

The nature of intramolecular charge transfer of N,N-diaryl dihydrophenazine photocatalysts (PCs) in different solvents is explored in context of their performance in organocatalyzed atom transfer radical polymerization (O-ATRP). PCs having a computationally predicted lowest energy excited state exhibiting charge transfer (CT) character can operate a highly controlled O-ATRP in a wide range of solvent polarities, from non-polar hexanes to highly polar N,N-dimethylacetamide. For PCs having a computationally predicted lowest energy excited state not possessing CT character, their ability to operate a controlled O-ATRP is decreased. This study confirms the importance of CT character in the excited state for N,N-diaryl dihydrophenazine PCs, and a deeper understanding of the activity of CT PCs has enabled the synthesis of polymers of low dispersity ( < 1.10) in a controlled fashion.

Organocatalyzed Atom Transfer Radical Polymerization: Perspectives on Catalyst Design and Performance.

The recent development of organocatalyzed atom transfer radical polymerization (O-ATRP) represents a significant advancement in the field of controlled radical polymerizations. A number of classes of photoredox catalysts have been employed thus far in O-ATRP. Analysis of the proposed mechanism gives insight into the relevant photophysical and chemical properties that determine catalyst performance. Discussion of each of the classes of O-ATRP catalysts highlights their previous uses, their roles in the development of O-ATRP, and the distinctive properties that govern their polymerization behavior, leading to a set of design principles for O-ATRP catalysts. Remaining challenges for O-ATRP are presented, as well as prospects for further improvement in the application scope of O-ATRP.

Intramolecular Charge Transfer and Ion Pairing in N,N-Diaryl Dihydrophenazine Photoredox Catalysts for Efficient Organocatalyzed Atom Transfer Radical Polymerization.

Photoexcited intramolecular charge transfer (CT) states in N,N-diaryl dihydrophenazine photoredox catalysts are accessed through catalyst design and investigated through combined experimental studies and density functional theory (DFT) calculations. These CT states are reminiscent of the metal to ligand charge transfer (MLCT) states of ruthenium and iridium polypyridyl complexes. For cases where the polar CT state is the lowest energy excited state, we observe its population through significant solvatochromic shifts in emission wavelength across the visible spectrum by varying solvent polarity. We propose the importance of accessing CT states for photoredox catalysis of atom transfer radical polymerization lies in their ability to minimize fluorescence while enhancing electron transfer rates between the photoexcited photoredox catalyst and the substrate. Additionally, solvent polarity influences the deactivation pathway, greatly affecting the strength of ion pairing between the oxidized photocatalyst and the bromide anion and thus the ability to realize a controlled radical polymerization. Greater understanding of these photoredox catalysts with respect to CT and ion pairing enables their application toward the polymerization of methyl methacrylate for the synthesis of polymers with precisely tunable molecular weights and dispersities typically lower than 1.10.

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst.

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism.

Organocatalyzed atom transfer radical polymerization driven by visible light.

Atom transfer radical polymerization (ATRP) has become one of the most implemented methods for polymer synthesis, owing to impressive control over polymer composition and associated properties. However, contamination of the polymer by the metal catalyst remains a major limitation. Organic ATRP photoredox catalysts have been sought to address this difficult challenge but have not achieved the precision performance of metal catalysts. Here, we introduce diaryl dihydrophenazines, identified through computationally directed discovery, as a class of strongly reducing photoredox catalysts. These catalysts achieve high initiator efficiencies through activation by visible light to synthesize polymers with tunable molecular weights and low dispersities.