Recent developments in the coordination chemistry of porphyrin complexes containing non-metallic and semi- metallic elements

The tremendous potential for the manifold applications of porphyrins, porphyrazines, and phthalocyanines derives from their photophysical and electrochemical properties, their remarkable stability, and their predictable and rigid structure. These applications include nonlinear optics, catalysts, sensors, actuators, molecular sieves, and therapeutics. All of these properties are modulated by appending various chemical moieties onto the macrocycles, by choice of metallo derivative, and by the choice of environment. In multichromophoric systems, furthermore, the relative orientation of the chromophores, the nature of the linker, and the size of the system also dictate the properties. The synthesis of multichromophoric systems – both via covalent and noncovalent linkers – is driven by the desire to make new materials and to understand biological processes such as the various aspects of photosynthesis. Though electron and energy transfer processes continue to drive the synthesis of ever more complex systems, more recent focus has shifted toward other applications and functionalities of these structures. The focus of this perspective is on four recent developments in formation and characterization functional, porphyrinic materials and devices: (1) self-assembly and self-organization of porphyrin arrays and aggregates into phototransistors and photonic devices; (2) self-assembled porphyrin squares for sensors, sieves, and catalysts; (3) spatially separated arrays of metalloporphyrins as stochastic sensors; and (4) covalently bound arrays of different chromophores as photonic materials.