Synthesis and applications of supramolecular porphyrinic materials

The supramolecular chemistry of porphyrinic systems is extraordinarily diverse because the rigid macrocycles offer a variety of topologies that can be matched to the topologies of hydrogen-bonding moieties and metal ion coordination geometries. Other modes to self-assemble multi porphyrin arrays and crystals exploit electrostatic interactions, combinations of hydrogen-bonding, and metal ion coordination. Porphyrinoids are ideal building blocks because they impart a high degree of functionality to the materials due to their rich electrochemical and photophysical properties, and their extraordinary stability. These properties will continue to be incorporated into supramolecular porphyrinic arrays and crystalline materials that can serve as the active components in sensors, molecular sieves, photonics, molecular electronics, and catalysts. Herein we summarize the various approaches to the synthetic supramolecular chemistry of porphyrins that results in discrete systems, and as a mode of crystal engineering. The functionality of many of these materials is discussed in relation to the supramolecular structure.