The Curious Case of a Parasitic Twin of the Corroles

An expanded porphyrinoid has been obtained by a simple ring expansion from a contracted porphyrinoid, namely corrole. Spectroscopic, structural, and computational investigations reveal peculiar π‐conjugation and geometry. The effect of extended π‐conjugation is evident from perturbed redox behavior and photophysical properties. Owing to the strong diatropic ring current of the corrole and cross‐conjugation, the molecule exhibits a non‐aromatic nature for the expanded π‐circuit, as evident from NMR studies. The curious case of a parasitic twin of the corroles: The π‐expansion of a GaIII–[18]corrole yields a hexapyrrolic expanded porphyrinoid with an aromatic and cross‐conjugated π‐circuit in a single molecular framework.