Heterocorroles: corrole analogues containing heteroatom(s) in the core or at a meso-position

Abstract

This review article presents an overview of the progress in heterocorrole chemistry including their syntheses, key structural aspects and properties.

Magnetic Diversity in Heteroisocorroles: Aromatic Pathways in 10-Heteroatom-Substituted Isocorroles

“…Isocorroles are a class of hybrid ligands that combine the diprotic character of porphyrins and the contracted N 4 cavity of corroles. − Heteroisocorroles (a term that we prefer over heterocorroles), in which the saturated meso carbon of isocorroles is substituted by a heteroatom, vastly expand the scope of these ligands. , Like other sterically constrained porphyrinoids, such as porphyrazines and corroles, 10-heteroisocorroles have been shown to stabilize unusual transition metal spin states, such as intermediate-spin Fe­(III), , whereas strong absorption in the red and near-infrared (IR) range may result in applications as near-IR dyes and in photodynamic therapy . Additionally, Bröring and co-workers have noted fascinating variations of aromatic character among 10-heteroisocorrole derivatives, characterizing the observations as “a welcome subject for future in-depth theoretical studies” …”

Synthesis of ABC‐Type 22‐Oxacorroles Bearing Three Different Five‐Membered Heterocycles at the meso Positions

“…[14][15][16] Core-modified corroles or heterocorroles are formally formed by replacement of one or two nitrogens of corrole with other heteroatoms such as S, O, Se, Si, Te and C. Such core-modified corroles show interesting physico-chemical and coordination properties that are different from all nitrogen-containing corroles. [17] Interestingly, a perusal of literature reveals that there are only limited reports available on core-modified corroles, [6][7][8][9][10][11][12][13] and all types of heterocorroles have not been synthesized because of lack of proper synthetic strategies, not so easily acces-sible precursors and also partly due to their inherently unstable nature. Johnson and co-workers in the late 1960s reported synthesis of dioxacorroles by adopting MacDonald type condensation.…”

Dual Emission of a Free‐Base 5‐Oxaporphyrinium Cation from its cis‐ and trans‐NH Tautomers

“…Consequently, 5[BAr F 4 ] exhibits a highly planar structure with a mean plane deviation of 0.041 . The lengths of the CÀ O bonds (1.362(4) and 1.365 (5)…”

“…One promising approach is the replacement of the meso-carbon(s) with heteroatom(s), which is known as the meso-modification strategy. [5] Meso-modification lowers the symmetry of the porphyrin core and strongly modulates its electronic structure depending on the intrinsic nature of the introduced heteroatoms. Consequently, meso-modified heteroporphyrins exhibit unique light-harvesting and electrochemical properties, magnetic behavior, and p-electron delocalization.…”