七元瓜环与1,7-二(2-苯并咪唑)庚烷的相互作用及自组装
收稿日期: 2015-09-11
修回日期: 2015-10-31
网络出版日期: 2015-11-06
基金资助
国家自然科学基金(No. 21272045)资助项目.
Interaction and Supramocular Self-Assembly of Cucurbit[7]uril with 2,2'-(Heptane-1,7-diyl) Dibenzimidazolium Chloride
Received date: 2015-09-11
Revised date: 2015-10-31
Online published: 2015-11-06
Supported by
Project supported by the National Natural Science Foundation of China (No. 21272045).
利用1H NMR法、紫外吸收光谱法、荧光发射光谱法和单晶X射线衍射等方法考察了七元瓜环(Q[7])与氯化1,7-二(2-苯并咪唑)庚烷(SBHt)在酸性溶液中的相互作用过程及组装模式. 首先考察了主客体相互作用对客体pKa的影响, 以确定研究主客体相互作用以及组装过程的实验条件. 1H NMR滴定实验结果表明, 在水溶液中主客体可形成1:1和2:1的主客体包结配合物, 当主客体物质的量之比为1:1时, Q[7]包结SBHt的烷基链, 两端苯并咪唑基团处于瓜环端口外侧; 当主客体物质的量之比为2:1时, 两个Q[7]分别包结同一SBHt分子的两端苯并咪唑基团, 这一实验结果得到荧光发射光谱的佐证. Q[7]与SBHt形成1:1的主客体包结配合物的晶体结构表明, 客体烷基链在瓜环空腔内发生折叠以使其通过离子偶极及氢键与Q[7]有效作用.
关键词： 七元瓜环; 1,7-二(2-苯并咪唑)庚烷; 相互作用; 超分子组装; 晶体结构
易君明 , 陈明华 , 薛赛凤 , 陶朱 . 七元瓜环与1,7-二(2-苯并咪唑)庚烷的相互作用及自组装[J]. 有机化学, 2016 , 36(3) : 653 -658 . DOI: 10.6023/cjoc201509015
The interaction and supramolecular self-assembly of cucurbit[7]uril (Q[7]) with 2,2'-(heptane-1,7-diyl) dibenzimidazolium chloride (SBHt) in aqueous solution were investigated by 1H NMR spectroscopy, fluorescence spectroscopy in details. The pKa shift of guest in the presence of Q[7] was first investigated in order to decide the pH of medium condition for investigation of host-guest interaction and supramolecular self-assembly. 1H NMR spectroscopy analysis revealed that Q[7] included the alkylene chain of guest and formed a simple 1:1 host-guest binding model complex at a low rate of NQ[7]/NSBHt, while at higher ratios of Q[7] to guest, two host Q[7] prefer to include the benzimidazolyl moieties of guest and formed a dumbbell shape inclusion complex. The typical reversible interaction modes were controlled by concentration of the ratio of host and guest, and the process was further conformed by fluorescence spectroscopy technology. The single X-ray crystal structure analysis showed a 1:1 host-guest inclusion complex in which the alkyl chain of SBHt was folded in order to effectively interact with Q[7] through ion-dipole interactions and hydrogen bonding.
[1] (a) Freeman, W. A.; Mock, W. L.; Shih, N.-Y. J. Am. Chem. Soc. 1981, 103, 7367.
(b) Day, A. I.; Arnold, A. P. WO 20068232, 2000 [Chem. Abstr. 2000, 133, 362775].
(c) Kim, J.; Jung, I. S.; Kim, S. Y.; Lee, E.; Kang, J. K.; Sakamoto, S.; Yamaguchi, K.; Kim, K. J. Am. Chem. Soc. 2000, 122, 540.
(d) Day, A. I.; Blanch, R. J.; Arnold, A. P.; Lorenzo, S.; Lewis, G. R.; Dance, I. A. Angew. Chem., Int. Ed. 2002, 41, 285.
(e) Cheng, X. J.; Liang, L. L.; Chen, K.; Ji, N. N.; Xiao, X.; Zhang, J. X.; Zhang, Y. Q.; Xue, S. F.; Zhu, Q. J.; Ni, X. L.; Tao, Z. Angew. Chem., Int. Ed., 2013, 52, 7252.
[2] (a) Fu, X. Z.; Shen, X. C.; Huang, Y.; Tao, Z.; Xue, S. F.; Zhu, Q. J. J. Guizhou Univ. (Nat. Sci.) 2007, 24(6), 650 (in Chinese). (傅晓钟, 沈祥春, 黄英, 陶朱, 薛赛凤, 祝黔江, 贵州大学学报(自然科学版), 2007, 24(6), 650.)
(b) Li, C., Li, J., Jia, X. Org. Biomol. Chem. 2009, 7, 2699.
[3] (a) Huang, Y.; Tao, Z.; Xue, S. F.; Zhu, Q. J. Chem. J. Chin. Univ. 2011, 32(9), 2022 (in Chinese). (黄英, 陶朱, 薛赛凤, 祝黔江, 高等学校化学学报, 2011, 32(9), 2022.)
(b) Lv, Y.; Yan, L. F.; Dong, L. Chin. J. Spectrosc. Spectral Anal. 2014, 34(6), 1610 (in Chinese). (吕研, 颜丽芬, 董兰. 光谱学与光谱分析, 2014, 34(6), 1610.)
(c) Wang, G. Q.; Guo, L.; Du, L. M.; Fu, Y. L. Microchem. J. 2013, 110, 285.
(d) Ma, D.; Hettiarachchi, G.; Nguyen, N.; Zhang, B.; Wittenberg, J. B.; Zavalij, P. Y.; Briken, V.; Isaacs L. Nat. Chem. 2012, 4, 503.
(e) Huang, Y.; Song, G. X.; Tang, Q.; Wang, J.; Tao, Z.; Xue, S. F. Chem. J. Chin. Univ. 2014, 35(6), 1224 (in Chinese). (黄英, 宋桂先, 唐青, 王娟, 陶朱, 薛赛凤, 高等学校化学学报, 2014, 35(6), 1224.)
[4] (a) Yang, J.; Du, L. M.; Wang, J. Q.; Wu, H.; Jing, X.; Liu, W. X.; Fu, Y. L. Anal. Chem. An Indian J. 2013, 12(4), 133.
(b) Zhao, G.; Wang, Z.; Wang, R.; Li, J.; Zou, D.; Wu, Y. Tetrahedron Lett. 2014, 55, 5319.
(c) Zhao, J.; Hu, S.; Zhong, W.; Wu, J.; Shen, Z.; Chen, Z.; Li, J. ACS Appl. Mater. Interfaces 2014, 6, 7070.
(d) Liang, L. L.; Zhao, Y.; Chen, K.; Xiao, X.; Clegg, J. K.; Zhang, Y. Q.; Tao, Z.; Xue, S. F.; Zhu, Q. J.; Wei, G. Polymers 2013, 5, 418.
(e) Farcas, A.; Aubert, P. H.; Mohanty, J.; Lazar, A. I.; Cantin, S.; Nau, W. M. Eur. Polym. J. 2015, 62, 124.
(f) Stucchi da Silva, L. F.; Leroux, F.; Taviot-Gúeho, C.; Valim, J. B.; Demets, G. J. F. Synth. React. Inorg. Met.-Org. Chem. 2013, 43, 1078.
(g) Ma, L.; Liu, S. M.; Yao, L.; Xu, L. J. Chromatogr. A 2015, 1376, 64.
(h) Wang, X.; Qi, M.; Fu, R. J. Chromatogr. A 2014, 1371, 237.
[5] (a) Xiao, L. W.; Li, L. L.; Gao, H. J.; Ren, P.; Kou, W.; Shi, Y. R. Chin. J. Org. Chem. 2014, 34, 2224 (in Chinese). (肖立伟, 李玲玲, 高红杰, 任萍, 寇伟, 时亚茹, 有机化学, 2014, 34, 2224.)
(b) Zhu, G. M.; Yang, L. Y.; Cui, D. M. Chin. J. Org. Chem. 2014, 34, 495 (in Chinese). (朱观明, 杨柳阳, 崔冬梅, 有机化学, 2014, 34, 495.)
[6] Ni, X. L.; Yi, J. M.; Song, S.; Zhang, Y. Q.; Xue, S. F.; Zhu, Q. J.; Tao Z. Tetrahedron 2013, 69, 6219.
[7] Guo, G. Y.; Tang, Q.; Huang, Y.; Tao, Z.; Xue, S. F.; Zhu, Q. Chin. J. Org. Chem. 2014, 34(11), 2317 (in Chinese). (郭改英, 唐青, 黄英, 陶朱, 薛赛凤, 祝黔江, 有机化学, 2014, 34(11), 2317.)
[8] (a) Yi, J. M.; Xiao, X.; Zhang Y. Q., Xue S. F., Tao Z., Zhang J. X. Acta Chim. Sinica 2014, 72, 949 (in Chinese). (易君明, 肖欣, 张云黔, 薛赛凤, 陶朱, 张建新, 化学学报, 2014, 72, 949.)
(b) Yi, J. M.; Ni, X. L.; Xiao, X.; Lv, L. B.; Xue, S. F.; Zhu, Q. J.; Tao, Z. Chin. Chem. Lett. 2013, 24, 362.
[9] Li, L. F.; Lin, Y. W.; Huang, Z. W.; Luo, H. B. Chem. J. Chin. Univ. 2012, 33, 282 (in Chinese). (李立凡, 林友文, 黄智文, 罗红斌, 高等学校化学学报, 2012, 33, 282.)
[10] Liu, M.; Cai, J. Langmuir 2000, 16, 2899.
/
| 〈 |
|
〉 |
