新型丁二炔-二酰胺大环化合物的合成及与TTF和DNP在溶液中的络合行为

高等学校化学学报 ›› 2010, Vol. 31 ›› Issue (7): 1353.

新型丁二炔-二酰胺大环化合物的合成及与TTF和DNP在溶液中的络合行为

周松根, 陈木娟, 唐明飞, 蒋腊生, 徐志锴, 张素辉, 梁吉东

华南师范大学化学与环境学院, 广州 510006

收稿日期:2009-10-23 出版日期:2010-07-10 发布日期:2010-07-10
通讯作者: 蒋腊生, 男, 教授, 主要从事超分子化学研究. E-mail: jianglsh@scnu.edu.cn
基金资助:
国家自然科学基金(批准号: 20672038)和广东省自然科学基金(批准号: 8151063101000015)资助.

Synthesis and Complexation Studies in Solution of Novel Diacetylene-diimide Cyclophanes

ZHOU Song-Gen, CHEN Mu-Juan, TANG Ming-Fei, JIANG La-Sheng*, XU Zhi-Kai, ZHANG Su-Hui, LIANG Ji-Dong

School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China

Received:2009-10-23 Online:2010-07-10 Published:2010-07-10
Contact: JIANG La-Sheng. E-mail: jianglsh@scnu.edu.cn
Supported by:
国家自然科学基金(批准号: 20672038)和广东省自然科学基金(批准号: 8151063101000015)资助.

摘要/Abstract

摘要：

由三甘醇和四甘醇出发, 经炔丙基烷基化、Mitsunobu反应和Eglinton偶联反应3步合成了2个含均苯四甲酸二酰亚胺结构单元以及丁二炔结构单元的大环化合物, 关环产率分别为81%和85%. 大环化合物及中间体的化学结构经核磁共振氢谱、碳谱、低分辨质谱、高分辨质谱或元素分析等确认. 通过氘代丙酮中¹H NMR实验以及氯仿中紫外滴定实验研究了这类大环化合物与客体分子四硫富瓦烯(TTF)和1,5-二甲氧基萘(DNP)在溶液中的相互作用, 结果发现, 大环化合物的核磁化学位移及紫外光谱均发生变化. 通过得到的主-客体间的络合常数可知, 此类新型大环化合物与TTF和DNP之间有一定的络合作用.

关键词: 大环化合物; 均苯四甲酸二酰亚胺; 丁二炔; 主-客体相互作用

Abstract:

Two new cyclophanes(3a, 3b) containing an aromatic diimide unit and a diacetylene unit were synthesized via alkylation reaction, Mitsunobu reaction, Eglinton coupling reaction in satisfactory total yield. Their structures were confirmed by NMR, ESI-MS, and elemental analysis or HRMS. Their complexation behavior in solution with TTF or DNP was investigated by means of ¹H NMR experiment in acetone-d₆ and UV experiment in CHCl₃. The chemical shift of protons of the cyclophanes and the UV absorption spectra were changed with the addition of TTF/DNP guests. The association constants of 3a/DNP and 3b/DNP are determined to be 20 and 24 L/mol, respectively, while the association constants of 3a/TTF and 3b/TTF are very small. These results indicate that these new cyclophanes can form complexes with TTF or DNP in solution, implying that they may be useful for constructing interlocked structures such as rotaxanes and catenanes.

Key words: Cyclophane; Pyromellitic diimide; Diacetylene; Host-guest interaction

TrendMD:

周松根, 陈木娟, 唐明飞, 蒋腊生, 徐志锴, 张素辉, 梁吉东. 新型丁二炔-二酰胺大环化合物的合成及与TTF和DNP在溶液中的络合行为. 高等学校化学学报, 2010, 31(7): 1353.

ZHOU Song-Gen, CHEN Mu-Juan, TANG Ming-Fei, JIANG La-Sheng*, XU Zhi-Kai, ZHANG S. Synthesis and Complexation Studies in Solution of Novel Diacetylene-diimide Cyclophanes. Chem. J. Chinese Universities, 2010, 31(7): 1353.

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