Structure–Property Relationships for Tailoring Phenoxazines as Reducing Photoredox Catalysts

• Published in: Journal of the American Chemical Society Vol. 140; no. 15; pp. 5088 - 5101
• Main Authors: McCarthy, Blaine G, Pearson, Ryan M, Lim, Chern-Hooi, Sartor, Steven M, Damrauer, Niels H, Miyake, Garret M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 18.04.2018; Amer Chemical Soc
• Subjects: Catalysis; catalysts; catalytic activity; Chemistry; Chemistry, Multidisciplinary; density functional theory; irradiation; Molecular Structure; molecular weight; Oxazines - chemistry; oxidation; Oxidation-Reduction; Photochemical Processes; photochemical reactions; Physical Sciences; polymerization; Polymethyl Methacrylate - chemical synthesis; Polymethyl Methacrylate - chemistry; polymethylmethacrylate; Quantum Theory; Science & Technology; Structure-Activity Relationship; white light; HALIDES; POLYMERS; ENERGY; MECHANISM; LIGHT; COMPLEXES; STATE; RADICAL POLYMERIZATION; POTENTIALS; ORGANIC SEMICONDUCTORS
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.7b12074

Through the study of structure–property relationships using a combination of experimental and computational analyses, a number of phenoxazine derivatives have been developed as visible light absorbing, organic photoredox catalysts (PCs) with excited state reduction potentials rivaling those of highly reducing transition metal PCs. Time-dependent density functional theory (TD-DFT) computational modeling of the photoexcitation of N-aryl and core modified phenoxazines guided the design of PCs with absorption profiles in the visible regime. In accordance with our previous work with N,N-diaryl dihydrophenazines, characterization of noncore modified N-aryl phenoxazines in the excited state demonstrated that the nature of the N-aryl substituent dictates the ability of the PC to access a charge transfer excited state. However, our current analysis of core modified phenoxazines revealed that these molecules can access a different type of CT excited state which we posit involves a core substituent as the electron acceptor. Modification of the core of phenoxazine derivatives with electron-donating and electron-withdrawing substituents was used to alter triplet energies, excited state reduction potentials, and oxidation potentials of the phenoxazine derivatives. The catalytic activity of these molecules was explored using organocatalyzed atom transfer radical polymerization (O-ATRP) for the synthesis of poly­(methyl methacrylate) (PMMA) using white light irradiation. All of the derivatives were determined to be suitable PCs for O-ATRP as indicated by a linear growth of polymer molecular weight as a function of monomer conversion and the ability to synthesize PMMA with moderate to low dispersity (dispersity less than or equal to 1.5) and initiator efficiencies typically greater than 70% at high conversions. However, only PCs that exhibit strong absorption of visible light and strong triplet excited state reduction potentials maintain control over the polymerization during the entire course of the reaction. The structure–property relationships established here will enable the application of these organic PCs for O-ATRP and other photoredox-catalyzed small molecule and polymer syntheses.