Abstract
A set of rotaxanes has been constructed consisting of a 30-membered macrocyclic ring, incorporating a 2,9-diphenyl-1,10-phenanthroline residue, threaded onto a second 2,9-diphenyl-1,10-phenanthroline residue with gold-(III) and zinc(II) porphyrins acting as terminal stoppers. The two chelating groups may be coordinated to copper(I) or zinc(II) cations or left free. Upon selective excitation of either porphyrin, rapid electron transfer occurs from the zinc porphyrin to the appended gold porphyrin and the ground state is restored by relatively slow reverse electron transfer. The rates of the various electron-transfer steps show a marked dependence on the molecular architecture and may be understood in terms of a frontier molecular orbital energy diagram involving through-bond electron or hole transfer
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