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The self-assembled macroring N -(Zn-Fb-Zn) 3 has been constructed by intermolecular complementary coordination among three trisporphyrin Zn-Fb-Zn molecules, each of which consists of a central free-base porphyrin and two imidazolyl-zinc-porphyrin ends. Thus, N -(Zn-Fb-Zn) 3 has three slipped-cofacial zinc porphyrin dimers (“special pair model”) and three free-base porphyrins, alternately. The zinc porphyrin dimers in N -(Zn-Fb-Zn) 3 are covalently connected by a ring-closing olefin metathesis reaction between the allyl ether groups substituted on the zinc porphyrin dimers, giving a covalently linked macroring C -(Zn-Fb-Zn) 3 . The fluorescence spectra of C -(Zn-Fb-Zn) 3 in several solvents show that the photoinduced energy transfer from one of the zinc porphyrin dimers to a free-base porphyrin occurs intramolecularly in toluene, whereas the photoinduced electron transfer predominantly occurs intramolecularly in N, N -dimethylformamide. Treatment of C -(Zn-Fb-Zn) 3 with copper(II) acetate gives a Cu-containing heteromultinuclear porphyrin macroring C -(Zn-Cu-Zn) 3, demonstrating that C -(Zn-Fb-Zn) 3 could be a good precursor to construct various heteromultinuclear porphyrin macrorings.
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Kuramochi et al. (2017) studied this question.
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