Synthesis and electrochemical investigations of molecular architectures involving C60 and tetraphenylporphyrin as building blocks
Synthesis and electrochemical investigations of molecular architectures involving C60 and tetraphenylporphyrin as building blocks
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以 C60 和四苯基卟啉为结构单元的分子结构的合成和电化学研究
DOI：
10.1039/a801079j
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发表时间：
1998
期刊：
影响因子：
--
通讯作者：
A. Rieker
中科院分区：
文献类型：
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作者：
Elke Dietel;A. Hirsch;Jinkou Zhou;A. Rieker
通过亲核环丙烷反应将卟啉锌与c60连接，制备了c60 -卟啉双体3a。用循环和差分脉冲伏安法在二氯甲烷中研究了富勒烯二联及其前体卟啉1a、2a。而C60没有观察到氧化峰，所有化合物1a-3a在EE机制方面表现出两个连续的准可逆氧化峰。由于在所有情况下卟啉环系统的氧化，所有三种的峰电位几乎一致。另一方面，在阴极过程中，化合物以准可逆的4次（C60）、2次（1a、2a）和5次（3a）单电子转移还原。与C60相比，3a的前两个形式电位（由C60部分产生）向负电位移动了40 mV，这是甲烷富勒烯的典型特征。除库仑效应外，3a中C60与卟啉部分之间几乎不存在电子相互作用。此外，还合成了含有四苯基卟啉锌的八面体加成结构的C60混合六加合物4。
A C60–porphyrin diad 3a has been prepared by connecting a zinc porphyrin and C60via nucleophilic cyclopropanation. The fullerene diad as well as the related precursor porphyrins 1a, 2a have been investigated by cyclic and differential pulse voltammetry in dichloromethane. Whereas no oxidation peaks were observed for C60, all compounds 1a–3a exhibit two successive, quasi-reversible oxidation peaks in terms of an EE mechanism. The peak potentials of all three species almost coincide, due to an oxidation of the porphyrin ring system in all cases. In the cathodic process, on the other hand, the compounds are reduced in quasi-reversible four (C60), two (1a,2a) and five (3a) one-electron transfers. The first two formal potentials of 3a (resulting from the C60 moiety) are shifted towards negative potentials by 40 mV, as compared to C60, which is typical for methanofullerenes. Aside from coulombic effects, there is almost no electronic interaction between the C60 and porphyrin parts in 3a. Furthermore, a mixed hexaadduct 4 of C60 with an octahedral addition pattern incorporating a zinc tetraphenylporphyrin has been synthesized.