meso‐Aryl [20]π Homoporphyrin: The Simplest Expanded Porphyrin with the Smallest Möbius Topology

An unstable conjugated homoporphyrin was successfully stabilized by introducing meso ‐aryl substitutents. It was evident from the moderate diatropic ring current found by NMR analysis that the newly formed 20π conjugated free base and its protonated form exhibited Möbius aromatic character. Furthermore, complexation as a ligand with an Rh^I ion afforded a unique binding mode and retained the Möbius aromaticity. Overall, these compounds are the smallest Möbius aromatic molecules, as confirmed by spectral and crystal‐structure analysis and supported by theoretical studies.