Oxidative Porphyrinoid Metamorphosis of Fourfold N‐Confused [32]Octaphyrin Bis‐Metal Complex to Doubly Linked 10‐Oxacorrole Metal Complex Dimer

We report an oxidative skeletal editing strategy that converts antiaromatic expanded porphyrins into structurally and electronically distinct porphyrinoids. Ni 0 ‐mediated cyclization of β,β′ ‐dibromotetrapyrrin metal complexes furnishes fourfold N‐confused (NC) [32]octaphyrin bis‐metal complexes that exhibit global antiaromaticity. Subsequent site‐selective oxidation at the inner α ‐positions triggers an unprecedented porphyrinoid metamorphosis, affording doubly linked 10‐oxacorrole metal complex dimers via oxygen incorporation and skeletal reorganization. Notably, these products display dual electronic structures in which locally aromatic 18π 10‐oxacorrole subunits are embedded within a globally antiaromatic 32π circuit, whereas diketo‐octaphyrin metal complex products show globally aromatic 30π systems. This transformation demonstrates that oxidative functionalization of NC frameworks enables precise control over both molecular topology and π‐electronic structure. These findings establish oxidative skeletal editing as a general strategy for inducing porphyrinoid metamorphosis and accessing previously unattainable aromaticity patterns.