一种冠醚金属卟啉化合物的合成及其阴离子识别机制  

Synthesis of Crown Ether Metal-prophyrin and Its Anion Recognition

作　　者：耿欣[1] 陈才[1] 李郭成 高康莉 邓兆静[1] 韩国志[1,2] 

机构地区：[1]南京工业大学理学院,南京210009 [2]东南大学分子电子学国家重点实验室,南京210096

出　　处：《应用化学》2015年第2期171-176,共6页Chinese Journal of Applied Chemistry

基　　金：东南大学生物电子学国家重点实验室开放课题(20111218)资助~~

摘　　要：合成了一种冠醚化卟啉化合物(1)及其Hg2+配合物(3),通过紫外光谱研究了冠醚卟啉化合物中卟啉单元与汞离子的配合性能,并采用核磁共振研究了其在溶液中的分子组装机制。利用冠醚环的离子识别行为以及冠醚环与卟啉环的协同作用,研究了冠醚金属卟啉化合物的阴离子识别检测,并对其机制进行了探讨。相比于5-(4-羧基苯基)-10,15,20-三苯基卟啉,冠醚卟啉化合物中的卟啉单元配合汞离子之后,其紫外吸收中的S带由415 nm红移至440 nm处。对于冠醚金属卟啉化合物而言,当其中的冠醚单元配合其特征金属阳离子之后,随着阴离子的不同,其紫外吸收光谱和颜色也呈现不同的特征,为阴离子的可视化识别提供了一种新的思路。A benzo-15-crown-5 modified 5-（4-carboxyphenyl）-10,15,20-triphenylporphyrin（1） was synthesized and used for binding with Hg2 ＋ion to form crown ether metal-prophyrin complex（3）. UV-Vis and1 H NMR were used to investigate the formation and self-assembly of complex 3. The difference of1 H NMR spectra of complexes 3 and 2 reveals that a synergy effect of prophyrin and crown ether exists. The anion recognition and mechanism of complex 3 were also studied. After addition of Na NH2,an obvious red shift in the UV-Vis spectra was observed accompanied with a color change from green to chartreuse viewed by naked eye. At the same time,the chemical shift of —CH2— in crown ether ring shifted from 3. 12 to 3. 16 and 3. 32 to 3. 34,respectively. This phenomenon can be explained by the strong nucleophilic property of amino anion.However,addition of other sodium salts such as Na Cl,Na H2PO4 and Na HCO3 could not result in the same phenomenon. This study provides a method for visible anion recognition.

关 键 词：冠醚 卟啉 合成 阴离子 可视化识别 

分 类 号：O621.2[理学—有机化学]