Tetrabromo[36]octaphyrin: A Promising Precursor of Directly Fused Porphyrin(2.1.1.1) Dimer and <i>meso‐α</i> Fused N‐Confused Porphyrin Dimer

3,7,23,27-Tetrabromo[36]octaphyrin 2 was synthesized as a novel octaphyrin bearing two meso-free positions. Surprisingly, its ZnII and NiII complexation reactions produced directly fused porphyrin(2.1.1.1) dimer 6, meso-α N-confused porphyrin (NCP) 7, the first example of NCP tape, respectively, via transannular C−C bond formation. While 6 exhibits diatropic ring-current effect owing to global 36π Möbius aromaticity, 7 shows paratropic due Hückel antiaromaticity. In addition, oxidation with PbO2 allowed for formation two-electron oxidized species 9 that exhibited 34π aromaticity. This work has demonstrated large expanded porphyrins can be promising platform produce porphyrinoids.