5,18‐Dimesitylorangarin: a Stable Antiaromatic [20]Pentaphyrin(1.0.1.0.0) Displaying Remarkable Oxidative Self‐Coupling Reactions

5,18‐Dimesitylorangarin and its BF2 complex were synthesized by double SNAr reaction of 3,5‐dibromo‐BODIPY with a‐(pyro‐2‐ly)dipyrrin as the first examples of meso‐aryl‐substituted orangarin. These orangarins, delineated as [20]pentaphyrin(1.0.1.0.0), are strongly antiaromatic but rather stable. The free base orangarin was coupled by oxidation with MnO2 to give a 11,11’‐linked dimer, a cyclooctatetraene(COT)‐centered trimer, and a spiro‐trimer. Fused COT‐centered 3H‐orangarin dimer was oxidized to the corresponding 2H‐orangarin dimer, which was further coupled to give a triply COT centered 2H‐orangarin tetramer. 3H‐Orangarin oligomers are all antiaromatic as evinced by extremely low‐field‐shifted 1H NMR signals of the inner NH and ill‐defined absorption spectra with broad tails. In contrast, COT‐centered 2H‐orangarin dimer and tetramer show moderately low‐field‐shifted NH signals and intense NIR absorbance over 900 nm, suggesting the effective p‐conjugation through the COT bridge and almost non‐antiaromatic character. These orangarin oligomers exhibit many reversible redox potentials owing to the intramolecular electronic interactions. Regardless of the different aromatic characters, all the orangarin monomers and oligomers exhibit very rapid excited‐state decays.