Kuramochi Yusuke, Kawakami Yuki, Satake Akiharu
Department of Chemistry, Faculty of Science Division II, Tokyo University of Science , 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Graduate School of Chemical Sciences and Technology, Tokyo University of Science , 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
Inorg Chem. 2017 Sep 18;56(18):11008-11018. doi: 10.1021/acs.inorgchem.7b01317. Epub 2017 Aug 25.
The self-assembled macroring N-(Zn-Fb-Zn) 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) 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) 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). The fluorescence spectra of C-(Zn-Fb-Zn) 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) with copper(II) acetate gives a Cu-containing heteromultinuclear porphyrin macroring C-(Zn-Cu-Zn), demonstrating that C-(Zn-Fb-Zn) could be a good precursor to construct various heteromultinuclear porphyrin macrorings.
自组装大环N-(Zn-Fb-Zn)是由三个三卟啉Zn-Fb-Zn分子通过分子间互补配位构建而成的，每个分子由一个中心游离碱卟啉和两个咪唑基锌卟啉端基组成。因此，N-(Zn-Fb-Zn)交替地具有三个错位共面的锌卟啉二聚体（“特殊对模型”）和三个游离碱卟啉。N-(Zn-Fb-Zn)中的锌卟啉二聚体通过锌卟啉二聚体上取代的烯丙基醚基团之间的闭环烯烃复分解反应共价连接，得到共价连接的大环C-(Zn-Fb-Zn)。C-(Zn-Fb-Zn)在几种溶剂中的荧光光谱表明，在甲苯中，光诱导能量从其中一个锌卟啉二聚体转移到游离碱卟啉发生在分子内，而在N,N-二甲基甲酰胺中，光诱导电子转移主要发生在分子内。用乙酸铜(II)处理C-(Zn-Fb-Zn)得到含铜的异多核卟啉大环C-(Zn-Cu-Zn)，表明C-(Zn-Fb-Zn)可能是构建各种异多核卟啉大环的良好前体。
