Unveiling N-Fused Nitreniums as Potent Catalytic Photooxidants.

The first example of a hitherto-unknown facet of catalytic photooxidant capability of nitrenium cations is reported herein. The fundamental limitation of inability of the traditional and reported nitreniums to achieve the excited-state redox potential beyond +2.0 V (vs Ag/AgCl), the primary requirement for a powerful photooxidant, is addressed in this work by developing a structurally unique class of N-fused nitrenium cations, with the required structural engineering involving extensive π-conjugation through ring fusion at the nitrenium site, which enabled significant lowering of the LUMO energy and easy reduction at the excited state (excited-state redox potential up to +2.5 V vs Ag/AgCl), facilitated by effective delocalization/stabilization of the generated radical. This finding opens a new way to discover novel and useful (photo)catalytic properties of nitrenium cations beyond just Lewis acidity.