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.