MOLECULAR DESIGN AND FUNCTIONS OF DENDRIMER PORPHYRINS

A series of aryl ether dendrimer porphyrin complexes were synthesized by a convergent approach. Iron porphyrin encapsulated within a large d endrimer framework reversibly bound dioxygen in the presence of 1-meth ylimidazole, where the resulting dioxygen adduct survived for more tha n 2 months even in the presence of water and (also) exhibited a high d urability toward carbonylation under carbon monoxide with a half-life as long as SO h. As a cytochrome c mimic, we also synthesized a water- soluble dendrimer zinc porphyrin with a negative-charged exterior surf ace ((-O2C)(32)L4PZn), which, upon mixing with a positive-charged elec tron acceptor such as methylviologen, formed a spatially separated don or-acceptor supramolecular assembly. Upon irradiation with visible lig ht, a long-range photoinduced electron transfer occurred through the d endrimer framework at a rate constant of 2.6 x 10(9) s(-1).