Synthesis of [34]Octaphyrin(1.0.1.0.1.0.1.0)

Abstract Ring‐expanded porphyrins are attracted because of their absorptions in the near‐infrared (NIR) region, redox behavior, and aromaticity. We have succeeded in the synthesis of planar ring‐expanded porphyrins starting from rigidified β,β’‐connected 2,2′‐bipyrrole. Octaphyrin(1.0.1.0.1.0.1.0) was synthesized by acid‐catalyzed condensation reaction of thieno[3,2‐ b :4,5‐ b ’]dipyrrole with pentafluorobenzaldehyde, followed by oxidation with p ‐chloranil. X‐ray crystallographic analysis showed the slightly ruffle‐distorted conformation. The nuclear magnetic resonance (NMR) and absorption spectra indicated the 34π aromatic character, which was supported by nucleus‐independent chemical shifts (NICS) calculations.