新型二芳烯有机框架化合物的设计、合成及构效关系研究

Diarylethenes are a novel type of functional material with excellent photochromic properties. Due to its high sensitivity and versatility for structural modification, there is a wide range of potential applications of diarylethenes in chemistry, materials science, and related fields. The unique structures and properties of organic framework compounds have been paid close attention to by both academia and industry. The researches on diarylthene-based organic framework compounds were carried out to widen their application range by endowing them with photo-responsive gas adsorption function. In this research proposal, novel diarylethene-based organic framework compounds, which can be trigged by light, will be designed. A serials of novel photoswitching organic framework compounds were synthesized based on: 1) preparing photoswitching covalent organic framework compounds by chemical reaction with compounds and diarylethenes that contain aldehyde group or amino group at the end; 2) using diarylethenes bridgehead functionalized of acyl chloride group and corresponding compounds to construct photoswitching organic framework compounds; 3) and constructing photochromic diarylethene covalent organic framework compounds by introducing the diarylethene to the functionalized side chain of the covalent organic framework compound. The influence of a variety of factors, such as functionalized diarylethene units, ligands on the optical properties of these novel diarylethene-based organic framework compounds will be systematic investigated, and the structure-activity relationship will be analyzed. Further structural modification and functionalization of these molecules will provide new diarylethene-based organic framework compounds with high sensitivity and improved fatigue resistance. Their applications in the field of photoswitching gas adsorption selectivity and related fields will also be explored. This research will provide theoretical basis and experimental accumulation for opening up a new way of light-controlled gas separation.

二芳烯是一类具有优异光致变色性能的新型功能化合物，具有灵敏度高和易于修饰等优点，在化学、材料科学等相关领域具有广阔的应用前景。有机框架化合物具有独特的结构与性能，受到学术界和产业界的密切关注。开展基于二芳烯有机框架化合物的研究，将赋予其光响应气体吸附功能，从而拓宽其应用范围。本项目拟采用新的设计思路，旨在开发具有光控分子开关特性的二芳烯有机框架化合物。以末端含醛基/氨基的二芳烯、二芳烯“桥头”为主链与对应结构单元构建光致变色二芳烯有机框架化合物；在共价有机框架化合物侧链引入光致变色二芳烯单元构建光致变色二芳烯共价有机框架化合物。系统研究二芳烯有机框架化合物的光致变色、比表面大小等性质与分子结构之间的构效关系；利用二芳烯有机框架化合物光致异构特性，获取高灵敏度的二芳烯有机框架化合物，并探讨其在光控气体吸附分离等领域的应用，为开辟光控气体分离新途径提供理论依据和实验积累。

二芳烯是一类性能优异的可逆光控响应功能材料，尤其是以全氟环戊烯为核心的二芳烯材料具有灵敏度高、抗疲劳性好及易于修饰等优点，在信息存储、防伪、光控气体吸附等领域具有广阔的应用前景。本项目主要在构筑二芳烯有机框架材料方面做了如下工作。.1.利用二芳烯侧方易于修饰的特点，在基于二芳烯与金属离子易于自组装的基础上，设计合成12种二芳烯金属Zn(II)、Cd(II)及Th(IV)有机框架化合物，且全部得到单晶结构，研究发现含氨基的二芳烯金属有机框架化合物对Kr的吸附能力最强，对Xe/Kr的吸附能力及保留时间均呈现倍数的关系。二芳烯Th(IV)有机框架材料具有显著的光控开关特性，0.1bar条件下，在开/关环状态下对Kr 的吸附量提升73.3%；同时光控开关对Kr/N2的分离由原来选择性大于100，扩大到翻倍的效果，该特性可用于核废料中Kr的分离。.2.利用末端含醛基全氟环戊烯与含氨基基团化合物合成二芳烯有机共价框架结构材料（COF），研究发现以 4,4',4'',4'''-(芘-1,3,6,8-四苯基) 四胺和 1,2-二[2-甲基-5-(4-醛基苯乙炔基)-3-噻吩基]全氟环戊烯合成的二芳烯COF，可实现光控开关对N2的吸附，光控开关比为2：1。该二芳烯共价有机框架化合物在关/开环态对 C2H2的吸附量提升80.9%，可实现光控C2H2的吸附分离。.3.该项目在合成上述二芳烯有机框架材料的基础上，探讨该类材料的分子结构、光致变色、比表面、光控吸附等性质，研究成果在Chem. Eng. J.、J. Solid. State Chem.、J. Rare Earth、Spectrochim. Acta A等国内外有影响力的期刊上，总计带本项目基金编号的SCI论文17篇，申请发明专利2项，获江西省自然科学奖一等奖1项。发表论文所采用的合成方法、提出的学术观点、科学方法、实验数据等被国内外多种学术期刊论文引用。此外，项目研究结果为进一步对光致变色二芳烯材料的研究和开发提供重要依据，也为其在框架结构领域进一步扩宽应用提供重要参考，对丰富光致变色二芳烯体系和有机框架材料体系具有重要意义和科学价值。