具有聚集诱导发光特性的多芳基取代多烯烃：分子设计、构效关系及其应用

As an emerging phenomenon and concept, aggregation-induced emission (AIE) changes the thoughts that aggregation of luminophores will cause quenching (ACQ). The investigation of AIE leads to the more in-depth exploration of the organic light-emitting mechanism and brings about profound changes in molecular design, preparation technique, regulation of aggregate structure, and device application etc. Polyenes substituted by multiple aryl groups, firstly explored by our group, possess AIE features thanks to their similar configurations to tetraphenylethene (TPE). Aryl-substituted polyenes linked with functional groups have been applied in chemo-sensors and bio-sensors, and exhibited single selectivity, high sensitivity and real-time responsibility. Based on our achieved results in this area, we will study the following issues in this proposal: continue study on molecular design, structure-properties relationship and applications of novel AIE-active aryl-substituted polyenes, especially those can emit red light with high emission efficiency; based on experimental data and theoretical calculation results by using modern characterization techniques and quantum calculation methods, clarifying the relationship between the intermolecular weak interactions and supramolecular hierarchical structure and thus improving the AIE mechanism and design principle; exploiting the application of AIE-active polyenes as advanced materials in chemo- and bio-sensors. Through the implementation of this proposal, we hope to establish a general design principle of AIE material system based on aryl-substituted polyenes with controllable structures and properties.

作为新现象和新概念，“聚集诱导发光 (AIE)”改变了人们关于聚集引起荧光猝灭的传统观念，引发了对有机发光机理更深入的探索，带来了分子设计、材料制备、聚集态结构调控及器件应用等方面的深刻变革。由我们率先研发的多芳基取代多烯烃已在化学与生物传感方面呈现出高灵敏、高选择性、实时响应等优势。本申请将以前期研究成果为基础，继续开展该系列化合物的设计与合成、构效关系及其应用研究，特别是实现高效发红光的多芳基取代多烯烃AIE化合物的构筑，确立AIE分子的设计原则；以实验结果为依据，通过应用现代表征技术和理论计算，阐明分子间弱相互作用机制与有机超分子多层次结构之间的关系，以揭示其AIE的化学与物理机制；开发基于多烯烃为中心的系列化合物在生物检测与影像、化学传感与响应等领域具有自主知识产权的先进功能材料。我们希望通过本申请能够建立一个结构与性能可调控、具有普适性的多芳基取代多烯烃AIE新体系。

作为新现象和新概念，“聚集诱导发光 (AIE)”改变了人们关于聚集引起荧光猝灭的传统观念，引发了对有机发光机理更深入的探索，带来了分子设计、材料制备、聚集态结构调控及器件应用等方面的深刻变革。由我们率先研发的多芳基丁二烯已在化学与生物传感方面呈现出高灵敏、高选择性、实时响应等优势。本项目的目的是进一步拓展该体系，并对聚集态下构效关系进行了研究，并通过各类官能团的引入实现了化合物功能可修饰性、发光波长可调性及其响应高效性，从而实现了对多氮唑、铈离子的高灵敏、特异性响应；建立了基于AIE原理的UV检测新方法；以植物纤维为晶种，利用温度升高增强结晶、光促分子内环化反应双重策略，实现了荧光强度对温度的正响应，为此提出了光/热增强发光的新概念；建立了血清中γ球蛋白免分离快速定量检测新策略，首次实现了在微观尺度下对肝实体瘤组织冰冻切片中肿瘤病灶的荧光快速鉴别，并建立了快速简便的诊断方法。经过四年的项目研究，得到了一系列基于多芳基取代丁二烯的综合性能优异且具有自主知识产权的关键性AIE发光材料，并提出。通过该项目的研究，更深入证明了分子内运动受限是产生聚集态下发光的主要机制，为构筑新的多芳基丁二烯AIE化合物，拓展应用新领域奠定了基础。项目执行期间发表论文22篇，其中含科普文章1篇，获得发明专利授权5件，提交申请1件；毕业博士生3名，硕士4名。本人作为唐本忠教授团队第三成员，获得2017年度国家自然科学一等奖。