聚集诱导发光配位聚合物晶态材料的制备及发光“开启”法检测VOCs的研究

This project will focus on the frontier of coordination polymers as sensors to detect small molecule. Up to now, the most common sensing of coordination polymers upon analytes with different characters is luminescence quenching (turn-off sensing). However, the turn-off sensing is limited and difficult to detect similar analytes, such as similar volatile organic compounds (VOCs). The materials with aggregation-induced emission (AIE) property can effectively break the limitation of the turn-off sensing, providing the possibility for detection of similar VOCs. In this program, a serious of AIE-CP crystalline materials will be designed and synthesized by assembly of 9,10-divinylanthracene derivative ligand and metal ion. The AIE-CP crystalline material for detection and capture of VOCs by turn-on sensing will be studied. The luminescence sensing properties of AIE-CP crystalline material will be enhanced with the variation of organic ligand and metal ions and the post-synthetic modification of AIE-CP. X-ray single-crystal diffraction will be used to directly visualize the precise and detailed structural information of AIE-CP before and after VOCs capture, which reveals single-crystal to single-crystal transformation. In combination with the theoretical calculation, the rule and mechanism between the detection ability and the structure of AIE-CP crystalline material will be explored. It is expected that the investigation of this project will lay a foundation for AIE-CP crystalline material as the probe for sensitive detection and capture of VOCs.

本项目主要着眼于配位聚合物（CP）检测小分子这一前沿方向。目前，CP主要是采用发光“关闭”法检测性质特殊的小分子，而性质相近的挥发性有机化合物（VOCs）则不易利用该法检测，这大大限制了CP检测小分子的范围。具有聚集诱导发光（AIE）性质的材料能够有效地突破发光“关闭”法的局限，为VOCs的识别提供了新的思路。本项目拟设计合成系列功能导向的二乙烯基蒽型衍生物配体，通过分子自组装与金属离子构筑系列AIE-CP晶态材料。研究这些化合物发光“开启”法检测VOCs的能力，通过配体和金属离子的改变及AIE-CP的后修饰来调控检测VOCs的灵敏度。利用X-射线单晶衍射技术表征捕获VOCs前后AIE-CP的微观结构信息，实现单晶-单晶转变，结合理论计算探索AIE-CP检测VOCs的机理及其构效关系与规律。通过本项目的研究，为制备发光“开启”法检测VOCs的AIE-CP晶态材料奠定坚实的理论和实践基础。

本项目着眼于配位聚合物晶态材料这一前沿领域。通过设计合成有机配体，合成功能性的配位聚合物，并对它们的性质进行研究。在项目执行期间，项目组成功合成多种有机配体，并基于这些有机配体成功合成三十余种配位聚合物（已发表数量），并对它们进行了表征。这些配位聚合物的结构被详细分析，并且分别对它们在荧光探针、光致变色、锂离子电池电极材料等方面的性质应用进行了深入研究。通过本项目的研究，为配位聚合物的实际应用提供了理论和实践基础。目前，在本项目的支持下，发表SCI学术论文 25 篇，其中项目负责人为第一作者或通讯作者的论文16篇。申请并授权发明专利1项。