Straightforward Dual Oxidative Cyclization Routes Enable Easy Access to Multifunctional Pyrrole-Fused Perylene Diimides

A dual route involving oxidants under heterogeneous conditions (PbO₂) or basic biphasic conditions, i.e., K₃[Fe(CN)₆]/KOH to C-N bond-forming pyrrole-fused PDIs is developed. These routes avoid the stringent conditions required for coupling reactions or other multistep processes used to date, to realize these functional PDIs. Importantly, both routes proceed at room temperature with short reaction times. In addition, the Br atom is tolerated during cyclization. These multistate redox-active pyrrole-fused PDIs generate blue-colored radical anions and red dianions chemically/electrochemically.