Kim Jong Seung, Shon Ok Jae, Yang Seung Hwan, Kim Jong Yeol, Kim Moon Jib
Department of Chemistry, Konyang University, Nonsan 320-711, Korea, Korea.
J Org Chem. 2002 Sep 6;67(18):6514-8. doi: 10.1021/jo0201169.
Two novel chromogenic 1,3-alternate calix[4]azacrown (1) and calix[4]-bis-azacrown (2) in which an indoaniline chromophore was attached on the nitrogen atom of the azacrown unit with one methylene spacer were synthesized. The 1H NMR spectrum of the ligand 1 and Ca2+ proved that the metal ion is entrapped by the calix[4]azacrown unit and by the conjugated indoaniline system. From the UV/vis band shifts upon metal ion complexation, Zn2+ ion was found to give the largest band shifts compared to other metal cations, indicating that Zn2+ ion (K(a) = 18 760 M(-)(1) for 1 and K(a) = 19 930 M(-1) for 2) was selectively encapsulated by the calix[4]azacrown cavity with assistance of the pendent indoaniline sidearm.
合成了两种新型生色的1,3-交替杯[4]氮杂冠醚（1）和杯[4]双氮杂冠醚（2），其中一个对亚苯基二胺发色团通过一个亚甲基间隔基连接在氮杂冠醚单元的氮原子上。配体1和Ca2+的1H NMR谱证明金属离子被杯[4]氮杂冠醚单元和共轭对亚苯基二胺体系所捕获。从金属离子络合时的紫外/可见光谱带位移发现，与其他金属阳离子相比，Zn2+离子引起的光谱带位移最大，表明Zn2+离子（1的K(a)=18760 M(-1)，2的K(a)=19930 M(-1)）在悬垂的对亚苯基二胺侧链的协助下被杯[4]氮杂冠醚空腔选择性包封。
