Metal-templated synthesis of 10-heterocorroles from dipyrrins

Corroles are ring-contracted aromatic porphyrinoids whose distinctive electronic structures arise from their direct pyrrole–pyrrole linkage and contracted macrocyclic framework. Incorporation of a heteroatom in place of a meso-carbon atom provides a versatile molecular design strategy for modulating the aromaticity, electronic structure, optical properties, redox behavior, and chemical reactivity of the macrocycle. This account summarizes our exploration of the chemistry of 10-heterocorroles, focusing on their molecular design, synthetic methodologies, structural characteristics, and electronic properties. Particular emphasis is placed on how the nature of the embedded heteroatom influences the macrocyclic electronic structure and, consequently, the aromaticity, optical properties, redox behavior, and reactivity of these porphyrinoids. Through the development of diverse heteroatom-incorporated frameworks, we have established 10-heterocorroles as a versatile platform for functional π-conjugated macrocycles with tailored electronic structures and properties.