第 47 卷第 4 期 Vol. 47 No. 4 2017 年 8 月 Aug 2017

所属栏目：功能材料 二茂铁苯并咪唑衍生物的合成及电化学性能研究与离子识别

刘亚坚，杨云峰*，李宇飞，冯彦梅，王世珍 （中北大学理学院，山西 太原 030051）

摘　要：以二茂铁为原料，经酰化反应得到二茂铁甲醛，再与含不同取代基的邻苯二胺进行加成、消除反应合成了3种二茂铁苯并咪唑衍生物FcB1~FcB3，通过1H NMR、13C NMR和IR表征其结构。采用循环伏安法、计时电流法和紫外可见光谱研究了3种二茂铁苯并咪唑衍生物的电化学性能和离子识别性能。结果表明，3种物质在电极表面均发生了单电子可逆氧化还原反应，且在电极表面的反应受扩散控制，扩散系数分别为1.201 cm2／s、1.533 cm2／s和2.190 cm2／s；在各种阴离子中，FcB1~FcB3对F-显示出多种信号响应识别，F-的加入使其紫外光谱448 nm处发生红移，吸光度增大，同时使其Fe3+／Fe2+电位分别向负极移动193 mV、174 mV、153 mV。核磁氢谱滴定结果表明，FcB1~FcB3中苯并咪唑环上的N-H质子与F-形成氢键从而达到识别功能。

关键词：二茂铁；苯并咪唑；循环伏安；紫外光谱；氟离子

中图分类号：O626　　文献标识码：A　　文章编号：1009-9212（2017）04-0059-06

Ferrocene Benzimidazole Derivatives：Synthesis, Electrochemical Properties and Ion Recognition

LIU Ya-jian, YANG Yun-feng*, LI Yu-fei，FENG Yan-mei, WANG Shi-zhen (School of Science, North University of China, Taiyuan 030051, China)

Abstract：In this paper, ferrocene was used as raw material to synthesis formaldehyde ferrocene by acylation reaction, and then reacted with different substituted o-phenylenediamines to give three ferrocene benzimidazole derivatives and marked as FcB1~FcB3, The structure was characterized by 1H NMR, 13C NMR and IR. The electrochemical properties and ion recognition of these ferrocene benzimidazole derivatives were studied by cyclic voltammetry, chronoamperometry and UV-visible spectroscopy. The results showed that the single electron reversible redox reaction occurred on the surface of the electrode, and the reaction was controlled by diffusion. The diffusion coefficients were 1.201, 1.533 and 2.190 cm2·s-1, respectively. Among various anions, FcB1~FcB3 showed a variety of signal responses to F-. The addition of F- gave a red-shift of its UV spectrum at 448 nm and the absorbance increased. At the same time, the Fe3+/Fe2+ potential was shifted to the negative electrode by 193, 174, and 153 mV, respectively. The results of NMR titration showed that the N-H protons on the benzimidazole ring of FcB1 to FcB3 could recognize the hydrogen-bonded F-.

Key words：ferrocene; benzimidazole; cyclic voltammetry; UV spectroscopy; fluoride ion

作者简介：刘亚坚（1993-），男，山西远城人，硕士研究生，研究方向：有机化学。

联 系 人：杨云峰，教授，有机合成及分子结构研究、功能高分子制备及性能研究（E-mail：yangyunfeng@nuc.edu.cn）。

收稿日期：2017-08-13