“…N,N′ -Disubstituted-dihydrophenazine derivatives are a class of highly electron-rich and redox-active building blocks and have attracted wide research interest due to their unique optical, electronic, magnetic, and chemocatalytic properties. For example, dihydrophenazine derivatives, especially N , N′ -diphenyldihydrophenazine ( DPPZ ), are easily able to form stable radical cation species under specific conditions, such as irradiation, heat, electrolysis, and chemical oxidation. − The easy to produce very persistent radical cation is one of the main advantages that makes DPPZ an emerging photocatalyst in various chemical transformations, especially visible light-driven reversible addition–fragmentation chain transfer (PET-RAFT) polymerization and metal-free atom transfer radical polymerization (ATRP). − The stable nature of the DPPZ radical cation also makes it ideal for the design of organic magnetic materials. , Notably, a number of studies have also illustrated that N , N′ -disubstituted-dihydrophenazines could undergo two single-electron oxidation processes accompanying the formation of radical cation and dication species (Scheme ). This special successive two-step, one-electron-transfer redox property renders DPPZ as an excellent active cathode material for the design of stable organic batteries. − However, compared to the well-studied radical cation of DPPZ , the dication species regarding to its real geometric and electronic structure and basic photophysical properties still remain a mystery.…”