フェロセニル基を軸末端に有するロタキサンのレドックス挙動と構造変化

概要

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In rotaxane chemistry, the control of the relative movement of the wheel component against the axle component is of current interest. In this paper, we wish to report the redox behavior of ferrocene-containing rotaxanes, and relative movement of the wheel component in the rotaxane driven by the redox reaction. A rotaxane bearing a ferrocene moiety was prepared by acylative end-capping of pseudorotaxane consisting of a crown ether and a secondary ammonium salt with ferrocenecarboxylic anhydride. Further acylation of the ammonium group gave the non-ionic rotaxane in which the wheel component is loosely restricted on the axle. Redox potential of the rotaxanes was measured using the cyclic voltammetry. The redox potential of the nonionic rotaxane was ca. 80 mV lower than that of other ferrocene derivatives. It was revealed that the oxidation of the ferrocene moiety was assisted by electron-donation from the crown ether moiety in the rotaxane. The attractive electrostatic interaction between the ferrocenium and crown ether moieties to give rise to the transposition of the wheel component on the axle is deduced.
基礎有機化学会（基礎有機化学連合討論会）の論文