Ferrocene-diyl Bridged Macrocages: Steric Effects of the Cage on the Redox Properties of Ferrocene Moiety
Ferrocene-diyl Bridged Macrocages: Steric Effects of the Cage on the Redox Properties of Ferrocene Moiety
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DOI：
10.1021/acs.organomet.8b00154
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发表时间：
2018-05
期刊：
影响因子：
2.8
通讯作者：
H. Takashima;Y. Inagaki;Hiroyuki Momma;Eunsang Kwon;K. Yamaguchi;W. Setaka
中科院分区：
文献类型：
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作者：
H. Takashima;Y. Inagaki;Hiroyuki Momma;Eunsang Kwon;K. Yamaguchi;W. Setaka
二茂铁/二茂铁鎓稳定的氧化还原性质已被用于研究二茂铁基功能材料。在此，使用循环伏安法测量的二茂铁二基桥接的大笼和它们的非笼异构体的外部笼的氧化还原性能的内部的双烯的空间效应进行了研究。由于半波电位（E1/2）取决于二茂铁稳定通过溶剂化，在E1/2的正位移中观察到的macrocage。由于阳极峰和阴极峰之间的电势的峰分离取决于电子转移的速率，由于外笼的绝缘效应，在macrocages中观察到从理想值的显著加宽。笼对二茂铁氧化还原性质的空间效应有助于二茂铁基功能分子的分子设计。
The stable redox properties of ferrocene/ferrocenium have been used to investigate ferrocene-based functional materials. Herein, the steric effects of an exterior cage on the redox properties of interior metallocenes have been investigated using cyclic voltammetry measurements of ferrocene-diyl bridged macrocages and their noncage isomers. As the half-wave potential (E1/2) depends on ferrocenium stabilization through solvation, positive shifts in the E1/2 were observed in the macrocages. As peak separation between potentials of the anodic and cathodic peaks depends on the rate of electron transfer, marked broadening from the ideal value was observed in the macrocages due to the insulating effect of the outer cage. These steric effects of the cage on the redox properties of ferrocenes could aid the molecular design of metallocene-based functional molecules.