Charge Separation in a Novel Artificial Photosynthetic Reaction Center Lives 380 ms

An extremely long-lived charge-separated state has been achieved successfully using a ferrocene−zincporphyrin−freebaseporphyrin−fullerene tetrad which reveals a cascade of photoinduced energy transfer and multistep electron transfer within a molecule in frozen media as well as in solutions. The lifetime of the resulting charge-separated state (i.e., ferricenium ion−C60 radical anion pair) in a frozen benzonitrile is determined as 0.38 s, which is more than one order of magnitude longer than any other intramolecular charge recombination processes of synthetic systems, and is comparable to that observed for the bacterial photosynthetic reaction center. Such an extremely long lifetime of the tetrad system has been well correlated with the charge-separated lifetimes of two homologous series of porphyrin−fullerene dyad and triad systems.