基于金属配位和主客体相互作用分级自组装构筑超分子凝胶

陶杰; 林翠玲; 王兆龙; 魏斌; 华奇侠; 万雪婷; 邱化玉; 尹守春

doi:10.11777/j.issn1000-3304.2017.16244

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基于金属配位和主客体相互作用分级自组装构筑超分子凝胶

研究论文 | 更新时间：2021-03-12

- 基于金属配位和主客体相互作用分级自组装构筑超分子凝胶
- The Construction of Supramolecular Polymer Gel by Hierarchical Self-assembly via Metal Ligand and Host-Guest Interactions
- 高分子学报 2017年第1期页码：93-100
- 作者机构：
  
  杭州师范大学材料与化学化工学院杭州 310036
- 作者简介：
  
  E-mail: yinsc@hznu.edu.cn Shou-chun Yin, E-mail:yinsc@hznu.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号21574034，2174034);浙江省自然科学基金(基金号LY16B040006);浙江省大学生新苗计划资助项目(项目号2016R423042)
- DOI：10.11777/j.issn1000-3304.2017.16244
  中图分类号：
- 纸质出版日期：2017-1，
  
  收稿日期：2016-8-2，
  
  修回日期：2016-9-18，
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陶杰, 林翠玲, 王兆龙, 魏斌, 华奇侠, 万雪婷, 邱化玉, 尹守春. 基于金属配位和主客体相互作用分级自组装构筑超分子凝胶[J]. 高分子学报, 2017,(1):93-100.

Tao Jie, Lin Cui-ling, Wang Zhao-long, Wei Bin, Hua Qi-xia, Wan Xue-ting, Qiu Hua-yu, Yin Shou-chun. The Construction of Supramolecular Polymer Gel by Hierarchical Self-assembly via Metal Ligand and Host-Guest Interactions[J]. Acta Polymerica Sinica, 2017,(1):93-100.
陶杰, 林翠玲, 王兆龙, 魏斌, 华奇侠, 万雪婷, 邱化玉, 尹守春. 基于金属配位和主客体相互作用分级自组装构筑超分子凝胶[J]. 高分子学报, 2017,(1):93-100. DOI： 10.11777/j.issn1000-3304.2017.16244.

Tao Jie, Lin Cui-ling, Wang Zhao-long, Wei Bin, Hua Qi-xia, Wan Xue-ting, Qiu Hua-yu, Yin Shou-chun. The Construction of Supramolecular Polymer Gel by Hierarchical Self-assembly via Metal Ligand and Host-Guest Interactions[J]. Acta Polymerica Sinica, 2017,(1):93-100. DOI： 10.11777/j.issn1000-3304.2017.16244.

摘要

将金属配位和主客体相互作用引入到同1个超分子体系中，设计合成了2个超分子单体

和

.通过这2个超分子单体分级自组装形成的交联网状超分子聚合物构建了一种多重刺激响应性和良好自修复性能的超分子凝胶.同时，进一步将具有聚集诱导发光性能的四苯乙烯引入到这种超分子体系中，以赋予超分子体系新颖的发光性能.单体分子

是由中间为双苯并24-冠-8的冠醚连接2个四苯基乙烯荧光生色团，两端为2个三联吡啶分子构成的1个主体分子.单体分子

两端的三联吡啶基团可以与过渡金属Zn（OTf）

进行金属配位形成线型超分子聚合物

；而中间的冠醚基团与双二级铵盐客体分子

通过主客体相互作用进一步形成交联超分子聚合物

.当该交联超分子聚合物的浓度达到30 mmol/L时，可形成荧光超分子聚合物凝胶.通过核磁共振（

H-NMR和DOSY）与黏度等测试方法，证明了线形和交联超分子聚合物的形成，并进一步通过流变的测试证明了超分子聚合物凝胶的形成及其良好的自修复性能.除此之外，由于引入的主客体相互作用以及金属配位固有的刺激响应性，该荧光超分子聚合物凝胶表现出对温度、pH值、K

离子和竞争配体的刺激响应性能.

Abstract

Two supramolecular monomers

and

were first designed and synthesized in order to introduce both metal ligand interaction and host-guest interaction into a same supramolecular system. A cross-linked supramolecular polymer was then formed by hierarchical self-assembly of these two supramolecular monomers

which were further constructed to form a supramolecular polymer gel with multiple stimuli-responsiveness and good self-healing properties. Furthermore

this supramolecular system also showed a strong fluorescence emission in the gel state due to the tetraphenylethene chromophore with aggregation induced emission property in the supramolecular system. As host molecule

monomer

as a host molecule was a dibenzo-24-crown-8 (DB24C8) moiety

with two tetraphenylethene fluorescent chromophores in the middle and two terpyridine units at both ends. Monomer

as guest molecule

was a bisammonium salt with two dibenzylammonium (DBA) units at both ends. After addition of metal ligand Zn (OTf)

into monomer

solution (

(CHCl

(CH

CN)=3:1))

monomer

formed a linear supramolecular polymer

based on the metal-ligand coordination interactions between terpyridine and Zn (OTf)

. By continuous addition of monomer

as cross-linker

the cross-linked supramolecular polymer

was obtained based on the host-guest interactions between DB24C8 and dibenzylammonium salt. The formations of the linear and the cross-linked supramolecular polymers were characterized by

H-NMR

DOSY and viscosity measurement. Furthermore

when the concentration of this cross-linked supramolecular polymer was increased up to 30 mmol/L

a fluorescence supramolecular polymer gel was constructed. The results showed that this fluorescent supramolecular polymer gel had a multiple stimuli-responsiveness (such as temperature

ions and competitive ligand) property

arising from the intrinsic characters of the metal ligand and host-guest interactions. The gel was characterized by fluorescence measurement and photograph method The results also showed that this new fluorescent supramolecular polymer gel was shown to have good self-healing property as confirmed by rheological test.

关键词

超分子聚合物超分子凝胶分级自组装多重刺激响应自修复

Keywords

Supramolecular polymerSupramolecular polymer gelHierarchical self-assemblyMultiple stimuli-responsivenessSelf-healing

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