新型含氮官能团光致变色二芳烯材料的制备及其性能研究

Diarylethenes are a novel type of optoelectronic functional materials with excellent photochromic properties. Due to its high sensitivity, thermal stability, fatigue resistance, and versatility for structural modification, diarylethenes have a wide range of potential applications in material science, environmental analysis, and related fileds. In this research proposal, novel designed prototype diarylethene molecules bearing nitrogen-containing functional groups will be synthesized, and a series of new photochromic materials based on: 1) diarylethenes with nitrogen-containing functional groups at bridgehead position， 2) polymeric nitrogen-containing diarylethenes, 3) diarylethenes with aromatic N-heterocycles at molecular scaffold or side chain position, will be prepared. The influence of a variety of factors, such as molecular structures, type of nitrogen-containing functional groups, substituting groups and their positions,on the optical properties of these novel diarylethene materials will be systematic investigated, and the structure-activity relationship will be analyzed. On the basis of UV absorption and fluorescence spetral change resulted from selective complexation of nitrogen atoms with metal ions, new nitrogen-containing diarylethenes with ideal properties will be identified as target molecules. Further structural modification and functionalization of these molecules will provide the resulting new materials with ultra high sensitivity, improved fatigue resistance, and strong fluorescence. Their applications in high-density information storage, cation recognition, and related fields, will be also explored.

二芳烯化合物是一类具有优异光致变色性能的新型光电功能材料，具有灵敏度高、热稳定性强、抗疲劳性好和易加工修饰等优点，在材料科学及环境分析等相关领域具有广阔的应用前景。本项目拟采用新的设计思路构建含氮原子功能性基团的二芳烯结构模型，制备系列新型含氮官能团二芳烯光致变色材料，主要包括：含氮官能团为桥头单元的二芳烯材料；含氮官能团二芳烯聚合物材料；含氮官能团为芳杂环骨架或侧链的二芳烯材料。系统研究分子结构、含氮官能团种类、取代基及取代位置等因素对其光电性质的影响，并分析总结其构效关系。利用含氮官能团与金属离子的选择性络合导致吸收光谱和荧光光谱显著变化的特性，筛选性能优良的目标分子进一步进行功能化修饰，获得具有高灵敏、耐疲劳和强荧光等优点的二芳烯材料，并探讨其在高密度信息存储和离子识别等领域中的应用。

作为一类具有优异光致变色性能的新型光电功能材料，二芳烯分子具有灵敏度高、热稳定性强、抗疲劳性能好和易加工修饰等优点。其优异的光开关效应引起的诸如荧光强度和吸收光谱、电化学性质、几何构型等分子性质的改变可用于设计多级稳定的开关材料，包括光调控的共聚物、荧光分子开关、光致变色的手性开关、光控传导开关和液晶开关等。因此，二芳烯分子在材料科学及环境分析等相关领域具有广阔的应用前景。本项目采用新的设计思路利用化学修饰方式构建几类列新型含氮官能团二芳烯光致变色材料：1）芳杂环骨架为含氮官能团的二芳烯化合物；2）侧基为含氮官能团的二芳烯化合物；3）多重调控功能的含氮官能团二芳烯化合物。并且详细研究了它们的分子结构、含氮官能团种类、取代基及取代基等因素对其光电性质的影响，分析其构效关系。利用含氮官能团与金属离子、有机小分子、无机阴离子或者酸碱选择性反应导致吸收光谱和荧光光谱的显著变化，获得一些具有高灵敏度、耐疲劳和强荧光的多重调控功能的二芳烯探针材料。项目执行期间，在Sensors and Actuators B: Chemical，J. Mater. Chem. C.，J. Phys. Chem. C.，Dyes Pigm.，RSC Adv.，NJC等杂志上共发表标注该项目基金号的SCI论文44篇，并且应邀在J. Mater. Chem. C. 上撰写题为“Recent advances in diarylethene-based multi-responsive molecular switches”的综述文章。申请授权三项专利。获得2016年江西省省自然科学二等奖。