双核开链茂铁咪唑受体的合成与阴离子识别研究  

Synthesis and Anion Recognition of Acyclic Ferrocene-Based Imidazole Receptors

作　　者：卓继斌[1] 晏希泉 王小雪[1] 谢莉莉[1,2] 袁耀锋[1,2] 

机构地区：[1]福州大学化学学院,福州350116 [2]能源与环境光催化国家重点实验室,福州350002

出　　处：《有机化学》2015年第5期1090-1096,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(Nos.21202019;21372043);国家基础科学人才培养基金(No.J1103303)资助项目~~

摘　　要：通过二茂铁甲基咪唑1与不同的二溴代烷反应合成了一系列双核开链的茂铁咪唑受体3a^3e,化合物3e的晶体结构表明分子间有着强的C—H…F氢键作用.利用电化学和核磁共振氢谱考察了受体3a^3e对不同常见阴离子的识别能力.电化学滴定实验表明受体3a^3e在乙腈溶液中均能很好地识别F-.核磁滴定证实了受体与不同阴离子之间氢键作用及参与类型.Job曲线表明受体分子与阴离子间形成1∶1型的配合物,通过络合常数(Ka)的对比表明受体3c对氟离子的选择性识别能力最好.The design and synthesis of artificial receptors capable of binding and sensing anions have been widely explored in the field of host-guest chemistry. Herein, a series of acyclic ferrocene-based imidazolium receptors 3a-3e were designed and synthesized. All the receptors were prepared by reactions of 1-（ferrocenylmethylene）imidazole 1 with corresponding dibromides in solvent under refluxing, followed by anion exchanges with NHaPF6. The structures of all the products were determined by IR, ^1H NMR, ^13C NMR, MS and elemental analysis. The crystal structure 3e was confirmed by X-ray crystallography, and it was clear that molecules were linked by C--H…F hydrogen bonds interactions. The interaction between these receptors and various anions was studied by electrochemical measurements and IH NMR spectroscopy. The receptors 3a-3e were proven to be highly selective and sensitive to F ^-. ^1H NMR titrations demonstrated that the receptors and anions form l ： 1 complex, and the receptors displayed a strong （C-H）^＋…X^- in anion recognition. Receptor 3e was the most effective receptor to bind with fluoride ion compared to the others.

关 键 词：二茂铁 开链 咪唑鎓 合成 阴离子识别 

分 类 号：O627.81[理学—有机化学]