基于刚性二苯乙烯的光响应超分子聚合物的构建和性能研究

Photoresponsive supramolecular polymers have been attracting much attention as new materials since they exhibit novel characteristics compared with conventional polymers. The key point in determining the performance of the photoresponsive supramolecular polymers is the properties of the photochromic unit (PU) in assembly building blocks. However, the types of PU currently employed are rather limited and their small geometric changes after irradiation or poor thermal stabilities restrain the development of supramolecular polymers. To solve these problems, three types of assembly building blocks with stiff stilbene as PU are designed, in which photoisomerization of the stiff stilbene will tune the shape of the building blocks, modulate between the intra- and inter-molecular interactions and lead to construction of the optical switching supramolecular material. The advantages of employing stiff stilbene as PU to construct photoresponsive supramolecular polymers involve their simple synthesis, large geometry differences between the two isomers,good thermal stability and good photoresponsiveness. This method is of potential for designing of novel photoresponsive assembly building blocks and stimuli-responsive polymers.

光响应超分子聚合物是目前超分子化学领域研究的热点，其组装基元中光敏感基团的性能是决定其光可控性的重要因素。文献报道的常见的光敏基团如二噻吩乙烯，偶氮苯等，具有光照前后构型变化小或者热稳定性差等缺点。本项目拟采用刚性二苯乙烯作为光敏基团，设计合成三类组装基元，利用刚性二苯乙烯的光顺反异构化反应改变组装基元的几何形状，从而改变其组装方式即分子内和分子间的相互作用，调控超分子聚合物的组装行为，构建光响应超分子聚合物材料。刚性二苯乙烯作为组装基元构建超分子聚合物具有合成简单，光照前后两种顺反异构体构型差异显著，热稳定性好和光响应性好等优点，利用该光敏基团有望构建新型光响应的组装基元和刺激响应超分子聚合物。

光响应超分子聚合物是超分子化学领域的研究热点，其组装基元中光敏感基团的性能是决定其光可控性的重要因素。本项目拟采用刚性二苯乙烯作为组装基元中的光敏基团，利用刚性二苯乙烯的光顺反异构化反应改变组装基元的几何形状和组装方式，调控超分子聚合物的组装行为，构筑光响应超分子聚合物材料。. 项目开展四年来，项目团队针对既定的研究目标认真开展了各项研究工作，全面完成了主要研究目标，取得了许多有意义的成果。发展了三类刚性二苯乙烯作为组装基元的超分子聚合物，包括：1）刚性二苯乙烯连接四重氢键组装基元的超分子聚合物；2）刚性二苯乙烯连接柱芳烃组装基元的超分子聚合物；3）刚性二苯乙烯连接冠醚组装基元的超分子聚合物。利用刚性二苯乙烯两种异构体的构型差异，有效利用光顺反异构化调控了超分子聚合物的聚合方式、聚合机制以及单向运动等，构筑了新型的光响应超分子聚合物。在此期间，培养了具有博士学位的研究生3人，具有硕士学位的研究生6人。在国内外刊物上发表论文18篇，其中IF >10.0的文章1篇，IF >3.0的文章8篇，包括Adv. Funct. Mater., Polym. Chem., Chem. Commun., Chem. Eur. J.等期刊；申请专利1项。