香豆素杯[]芳烃合成及其锌(II)配合物光谱.docVIP

香豆素杯[4]芳烃合成及其锌(II)配合物光谱?摘 要：为探寻对过渡金属离子具有配合作用的新型超分子配体，将杯［4］芳烃经醚化、氨解得到的中间体3与香豆素-3-甲酰氯反应，合成了新的含香豆素片段的杯［4］芳烃配体H?2L，用?1HNMR、??13?CNMR、IR、MS(Maldi -Tof) 表征其结构。H?2L与醋酸锌反应，获得了相应锌(II)配合物(LZn)，元素分析及MS(ESI)分析结果表明，LZn的化学组成为L(ZnAc)?2#8226;2H?2O。研究了锌(II)配合物的UV和IR吸收光谱性质，还测定了它的荧光强度。结果表明，与H?2L相比，锌(II)配合物分子中共轭体系增大且平面刚性增加。? 关键词：香豆素杯［4］芳烃衍生物; 锌(II)配合物; 光谱性质? 中图分类号：O621.3文献标识码：A [WT]文章编号：1672-1098(2011)02-0056-05?? ? 收稿日期：2010-12-23? 基金项目：安徽理工大学博士科研基金资助项目(DG541)。? 作者简介：王飞(1985-)，男，安徽六安人，在读硕士，研究方向：精细化学品。? [JZ(〗[WT3BZ]Synthesis of Coumarin-Calix［4］arene Derivative and ?Spectral Properties of Its Zn(II) Complex? WANG Fei, ZHANG Xiao-mei, XU Guo-cai? (School of Chemical Engineering , Anhui University of Science and Technology, Huainan Anhui 232001, China)? Abstract: In order to seek a new supramolecular ligand with the capacity for coordination to transition metal ions, a new calix［4］arene derivative H?2L with coumarin sections was synthesized by the reaction of coumarin-3-formyl chloride with intermediater 3 prepared by etherification firstly and then ammonolysis of calix［4］arene, and its structure was characterized by ?1HNMR, ??13?C NMR, IR and MS (Maldi-Tof). Reacting H?2L with zinc acetate could produce a Zn(II) complex (LZn), and the chemical composition of LZn was L(ZnAc)?2#8226;2H?2O determined by elementary analysis and MS(ESI). Using IR and UV, the absorption spectra of LZn were studied, and the fluorescence intensity was examined also. Results showed that conjugation system in LZn was enlarged and plane rigidity increased by comparison with those in H?2L. ? Key words:coumarin-calix［4］arene derivative; Zn(II) complex; spectral property?? 杯芳烃作为第三代主体分子， 以其为结构平台构筑杯芳烃无机杂化超分子配合物并进行性能研究是近年新的研究热点??［1］?。锌是与生命过程密切相关的重要金属元素之一，因此，具有识别锌(II)的新型杯芳烃衍生物的设计合成及其在分析、分离及酶催化反应等性质上研究一直受到国内外学者的重视??［2-7］?。本文在文献［8］基础上，设计合成了含香豆素片段杯［4］芳烃衍生物配体H?2L (见图1)，初步研究H?2L与醋酸锌反应产物锌(II)配合物的光谱性质，为其在光学及分析分离领域的应用提供基础实验数据 (1) KI,CICH?2COOEt;(2) NH?2.H?2O;(3) C?9H?5O?2-COCI? 图1配体