Formation and applications of stable 10 nm to 500 nm supramolecular porphyrinic materials

Nanoscaled materials of organic dyes are of interest for a variety of potential applications because of the rich photonic properties that this class of molecules can impart. One mode to form such nanoscaled materials is via self-organization and self-assembly, using reasonably well understood methods in supramolecular chemistry. But there are inherent complexities that arise from the use of organic-based supramolecular materials, including stability toward dioxygen, structural stability, and nanoarchitectures that may change with environmental conditions. Porphyrinoids have rich photonic properties yet are remarkably stable, have a rigid core, are readily functionalized, and metalation of the macrocycle can impart a plethora of optical, electronic, and magnetic properties. While there are many <10 nm porphyrinic assemblies, which may or may not self-organize into crystals, there is a paucity of 10–500 nm porphyrinic materials that can be isolated and stored. A variety of strategies towards the latter nanoscopic porphyrinic materials are discussed in terms of design, construction, and nanoarchitecture. The hierarchical structures include colloids, nanorods, nanotubes, nanorings, and nano-crystalline materials. This prolegomenon emphasizes the supramolecular chemistry, structure-stability, and structure-function relationships. The goal herein is to examine general trends and delineate general principles.