Synthetic Expanded Porphyrin Chemistry

Expanded porphyrins are synthetic analogues of the porphyrins, and differ from these and other naturally occurring tetrapyrrolic macrocycles by containing a larger central core with a minimum of 17 atoms, while retaining the extended conjugation features that are a hallmark of these quintessential biological pigments. The result of core expansion is to produce systems with novel spectral and electronic features, interesting and, often unprecedented, cation‐coordination properties, and, in many cases, an ability to bind anions in certain protonation states. Also adding to the appeal of expanded porphyrins is their central role in addressing issues of aromaticity. In many cases, they also display structural features, such as decidedly nonplanar “figure‐eight” motifs, that have no antecedents in the chemistry of porphyrins or related macrocyclic compounds. In this Review, the various synthetic approaches now being employed to produce expanded porphyrins as well as their various applications‐related aspects are discussed.