Porphyrinoids: Highly Versatile, Redox‐Active Scaffolds for Supramolecular Design and Biomimetic Applications

Abstract

Porphyrinoids are a growing class of oligopyrrole macrocycles that have structural and physical properties additional to those of the traditional tetrapyrrolic porphyrin macrocycles. In this chapter, after an initial description of how the porphyrins have been adapted for self‐assembly and supramolecular synthesis, we describe several aspects of porphyrinoid supramolecular systems, finally focusing on the use of an oxoporphyrinogen core as a scaffold for assembling complex oligochromophoric manifolds by using a combination of synthetic and coordination chemistries. An important feature of porphyrinoids is their increasing amenability to core functionalization, unlike the porphyrins in which peripheral derivatization has been the usual method for augmentation. Core functionalization introduces different molecular morphological possibilities for the porphyrinoids complementary to those available for the porphyrins. In fact, porphyrins and porphyrinoids can be agglomerated in supramolecular assemblies to exploit the functional and synthetic properties of both sets of compounds.