meso – meso ‐Linked Diarylamine‐Fused Porphyrin Dimers

A meso – meso ‐linked diphenylamine‐fused porphyrin dimer and its methoxy‐substituted analogue were synthesized from a meso – meso ‐linked porphyrin dimer by a reaction sequence involving Ir‐catalyzed β‐selective borylation, iodination, meso ‐chlorination, and S N Ar reactions with diarylamines followed by electron‐transfer‐mediated intramolecular double C−H/C−I coupling. While these dimers commonly display characteristic split Soret bands and small oxidation potentials, they produced different products upon oxidation with tris(4‐bromophenyl)aminium hexachloroantimonate. Namely, the diphenylamine‐fused porphyrin dimer was converted into a dicationic closed‐shell quinonoidal dimer, while the methoxy‐substituted dimer gave a meso – meso , β‐β doubly linked porphyrin dimer.