Iodine(III)‐Induced Cascade Annulation of <i>β</i> ‐Cyanoporphyrins for the Efficient Synthesis of <i>N</i> ‐Aryliminonaphtho‐Fused and <i>N‐</i> Aryl‐Carboxamide Porphyrins

Meso‐β fused porphyrins with tunable optoelectronic properties are attractive candidates for applications in light‐harvesting, sensing, and catalysis, yet their synthesis often requires harsh conditions or tedious synthetic routes. Herein, a mild, operationally simple, and Cu(OTf) 2 ‐catalyzed protocol is reported to access meso‐N ‐aryliminonaphtho‐fused and N‐ arylcarboxamide porphyrins from readily available β ‐cyanoporphyrins and diaryliodonium salts. Reaction selectivity is controlled by the water content present in the reaction mixture, affording either fused imines or carboxamides in high yields. The protocol tolerates different symmetrical diaryliodonium salts and enables the preparation of free‐base, Zn (II), and Cu (II) porphyrin derivatives, all fully characterized by NMR, UV–visible spectroscopy, high resolution mass spectrometry, electrochemistry, and single crystal X‐ray diffraction. The π‐extended systems exhibit distinct bathochromic shifts (≈42 nm in Soret and ≈80–90 nm in Q‐bands) and narrowed highest molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gaps up to 1.54 eV. Electrochemical studies reveal that fused porphyrins exhibited anodically shifted reduction potentials, while Density functional theory calculations attribute the gap reduction to LUMO stabilization and HOMO destabilization induced by fusion. Overall, this strategy provides rapid access to structurally diverse π‐extended porphyrins with tailored photophysical and redox properties.