自由基堆积驱动的动态共价键聚合物折叠与聚集

项目名称： 自由基堆积驱动的动态共价键聚合物折叠与聚集

项目编号： No.21472023

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 张丹维

作者单位： 复旦大学

项目金额： 80万元

中文摘要： 本项目提出利用酰腙和双硫键动态共价键的形成，快速合成并入紫精和四硫富瓦烯（TTF）的13个聚合物结构体系。紫精和TTF单元通过柔性乙氧基链或刚性芳酰胺连接。进一步还原紫精或氧化TTF为正离子自由基，构筑相应的自由基聚合物体系。通过正离子自由基分子内堆积作用诱导构筑褶皱状人工折叠结构，利用其分子间堆积构筑双股及多股自组装结构。利用碱金属离子-乙氧基链之间的络合作用促进正离子自由基分子内堆积及相应折叠结构的形成。利用刚性连接片段抑制分子内堆积，促进分子间堆积和相应层状聚集体的形成。利用供体-受体相互作用构筑聚轮烷体系，通过还原紫精或氧化TTF构筑多重正离子自由基组装体，研究组装体内不同类型正离子自由基的堆积性质及相关动力学性质。发展新的人工折叠结构及新的超分子自组装驱动力模式。

中文关键词： 超分子化学；自组装；自由基；分子折叠；堆积

英文摘要： In this project,we propose constructing 13 series of viologen (V) or tetrathiafulvalene (TTF)-incorporated polymers through the formation of dynamic hydrazone or disulfide bonding. The V or TTF units will be connected by flexible oligo(ethylene glycol) chains or rigid aromatic amide linkers. The V and TTF units will be converted to their radical cation through selective reduction (for V) or oxidation (for TTF). The intramolecular stacking of the radical cations will be utilized to induce the backbones to form pleated foldamers, while their intermolecular stacking will be used to induce the backbones to produce duplexes or more complicated aggregates. Alkali metal ions will be utilized to promote the formation of the folded conformation by binding to the oligo(ethylene glycol) chains. Pseudorotaxane polymers will also be constructed based on donor-acceptor interaction. The V and/or TTF units in these interlocked systems will be converted to their respective radical cations. Their stacking in the interlocked systems will also be studied. From this project, new folded polymers will be constructed and the stacking of aromatic radical cations will be investigated systematically, which would lead to the development of new useful binding patterns for supramolecular self-assembly.

英文关键词： supramolecular chemistry;self-assembly;radical;folding;stacking