Synthesis and Reduction of Nitrogen-Substituted Diaryl Dihydrophenazine Diradical Dications

A one-pot synthetic approach to form core-extended N,N′-disubstituted diaryl dihydrophenazine (DADHP) diradical dications (DRDCs) via chemical oxidation from aryl-substituted ortho-phenyldiamines is reported. The isolated N,N′-disubstituted DADHP DRDCs were reduced to their neutral counterparts with hydrazine. The model system featuring an unsubstituted fluorene aryl group, 2a, was tested as a photocatalyst for the polymerization of methyl methacrylate using organocatalyzed atom transfer polymerization (O-ATRP), which yielded a polymer with a controlled molecular weight and narrow polydispersity.