More confused than ever: Three types of N‐confused corrole isomers (NCCs) were synthesized, and the structures of these isomers were revealed by single‐crystal X‐ray crystallography. The position of the confused pyrrole ring in the NCC has a pronounced effect on optical and anion‐binding properties.

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Oxidative cyclization of a doubly N-confused bilane afforded a N-confused N,C-linked corrole (N-confused norrole), which was readily oxidized to form a C-fused N,C-linked corrole (C-fused norrole).

Ein neuer Dreh: Drei Arten N‐invertierter Corrolisomere (NCCs) wurden synthetisiert, und ihre Strukturen wurden mithilfe von Einkristall‐Röntgenstrukturanalyse aufgeklärt. Die Position des invertierten Pyrrolrings im NCC wirkt sich stark auf die optischen Eigenschaften und die Anionenbindung aus.

Novel near-infrared phosphorescent iridium(III) complexes based on benzo-annulated N-linked corrole analogue (termed as benzonorrole) were synthesized. The structures of the complexes revealed octahedral coordination geometries involving an organometallic iridium-carbon bond with two external axial ligands. Interestingly, the iridium(III) complex exhibits near-infrared phosphorescence at room temperature at wavelengths beyond 900 nm. The significant redshift of the emission, as compared to the corrole congener, is originated from the ligand-centered triplet character. The fine-tuning of the photophysical properties of the complexes was achieved by introducing electron-donating and electron-withdrawing substituents on the axial pyridine ligands.