Photoinduced electron transfer in multiporphyrin clusters and rotaxanes

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Abstract
A zinc(I1) porphyrin and a gold(II1) porphyrin dimer bridged by a 2,9-diphenyl-l, 10-phenanthrolin e (dpp) spacer has been synthesized in order to mimic the array of tetrapyrrolic chromophores in the bacterial photosynthetic centres. The electronic properties of the dpp bridge have been tuned by complexation o f copper(1) either in a hornoleptic, entwined complex, or i n a rotaxane complex whose threaded ring is a dpp-containing m acrocycle. Photoinduced electron transfer between the zinc porphyrin excited state and the gold porphyrin cation has been studied by laser f lash spectroscopy and its rate has been shown to depend on the nature of the bridging s pecies lying in between the metal porphyrins : 55 ps in the dpp- bridged dimer, a nd 1 ps only in the rotaxane copper(1) complex.

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