富电子共轭配合物对硝基爆炸物的识别、检测及器件研究

Research on the chemosensors for fast/ultratrace recognitions and detections of explosives has attracted great interests because the exploration of nitroaromatic sensors is very significant in preventing terror raids, detecting landmines and evaluating the circumstance hazards of the ammunition. Many important achievements have been obtained in this field. However, the regulatory mechanisms and influence factors of the recognition properties for nitroaromatic compounds are still unclear and necessary to be further investigated. In this project, we are planning to prepare a family of transition-metal complexes as fluorescent probes, which are based on various conjugated ligands with different molecular lengths, conformations, symmetries and substituents. The performance optimization studies on different electron structures as well as spectral, electrochemical and charge-transfer properties for related compounds before and after the metal-ion complexation will be carried out for full comparisons, which provide a solid theoretical foundation for the design and synthesis of transition-metal complexes having well-defined conjugated ligands. Furthermore, some experimental methods, such as fluorescence titration, co-crystallizing growth and self-assembled monolayer, will be performed to elucidate the detection properties and device performances of our compounds controlled by the structure factors and supramolecular interactions (intermolecular hydrogen bonding and π-π stacking interactions, and so on), and facilitate the investigations on their structure-function relationships. The results could further reveal the regulatory mechanisms of luminescent properties and provide the research and development of visual chemosensors with scientific reference and guidance.

芳香硝基爆炸物快速而灵敏的识别与检测在预防恐怖袭击、探测地雷以及评估军火的环境风险等方面发挥重要的作用，因而引起了人们极大的兴趣。虽然各国科学家在这一领域已经取得了许多非常重要的成果，但是硝基芳烃类化合物识别性能的调控机制和影响因素仍不清楚，需要进一步探索。在本项目中，欲通过配体的共轭长度、空间构型、构造对称性、封端基团的富电子能力变化，深入比较配位前后分子性能的改变，调节分子内电荷转移特性，控制传感器的荧光性能，探讨电子授受作用对于体系荧光猝灭的程度，为富电子共轭配合物的设计和合成奠定坚实的理论基础。欲通过溶液荧光滴定、共晶生长、玻片负载等手段研究有机/配合物在不同的介质中对于缺电子硝基芳烃体系的识别，探讨分子间氢键、π-π堆积、空间位阻、取代基效应等因素对于识别效能的影响，揭示富电子共轭体系发光性能的调控机制，为开发可视化的传感器件提供科学依据。

本项目紧紧围绕芳香硝基爆炸物快速而灵敏的识别与检测这一课题开展工作，采用配体与配合物对比、聚集诱导发光调控、可视化试纸制备等手段，集中探索了传感器识别性能的调控机制和影响因素，取得了系列研究进展。在本项目的资助下，所制备的一系列新型功能材料和传感器件，通过红外波谱、核磁共振、X-射线单晶衍射、扫描电子显微镜等多种现代检测手段的充分表征，为富电子共轭材料的设计和合成奠定坚实的理论基础，为开发可视化的传感器件提供科学依据。三年来，在国内外主流学术刊物如Sensors and Actuators B, J. Phys. Chem. C, ACS Appl. Mater. Interfaces等发表标注有国家基金资助的论文15篇，其中1区Top期刊2篇；发表会议论文2篇；获得授权国家发明专利4项。一些成果得到了审稿专家的肯定，同行专家的引用，并通过了第三方验收专家的验收，顺利完成了预期的研究目标。