In recent years, the field of porphyrin chemistry has expanded to include several new analogs of the original four pyrrole, carbon-bridged systems. This review traces the development of one such class of new macrocycles, namely Schiff-base porphyrin analogs. The review's focus is on the synthesis and properties of these new Schiff-base macrocycles that for ease of division have been divided into four classes: systems with two pyrrole rings, systems with three pyrrole or heterocyclic rings, systems with four pyrrole or heterocyclic rings, and systems with five or more pyrrole or heterocyclic rings. In addition to the role of metal ions as templating agents in the synthesis of these complexes, the rich coordination chemistry of several of the macrocycles is also discussed. X-ray crystallography has played an important role in determining the structures of many of these Schiff-base porphyrin analogs and many of the available structures have been incorporated into this review. Aromaticity of the macrocycles is discussed and has been evaluated from available electronic and NMR spectra. Finally, several potential applications of these molecules are discussed, briefly.
Structural studies of Schiff-base [2 + 2] macrocycles derived from 2,2′-oxydianiline and the ROP capability of their organoaluminium complexes