芳香多羧酸稀土簇基配合物类线性荧光探针的合成及其识别农药残留的研究

As one of the significant molecules-based functional luminescence materials, aromatic multicarboxylate ligands-based lanthanide coordination polymers (LnCPs) have been drawing immense interest because of the advantages combining Ln ions and multicarboxylate ligands, as well as their potential applications in luminescent materials, fluorescence sensors and biological detection. This project would design and synthesize aromatic multicarboxylate ligands with specific symmetries and coordinated groups with the help of organic synthesis, and then reacting with Ln clusters to construct multicarboxylate ligands-based LnCPs. The chemical compositions and crystal structures would be determined accurately, and the reaction factors effects on the final products including the starting reagents and proportions, reaction solvents, temperature and pressure, as well as pH values would be fully explored. Meanwhile, the formative conditions and structural features of the targeted LnCPs would be systematically studied, which could provide the theoretical basis for controllably designing and preparing cluster-based LnCPs containing multicarboxylate ligands. The sensibility of the probes can be effectively adjusted through introducing other different metal ions (transition-metal ions or Ln ions) and adjusting the proportion of doped metal ions into one system. We would mainly investigate the linear fluorescence probes for the recognition and quantitative analyses of pesticide residues and other environmental pollutants. Furthermore, the recognition mechanism would be clarified. The project is intended to controllable synthesis luminescent cluster-based LnCPs through employing special aromatic multicarboxylate ligands and Ln clusters with unsaturated coordination sites, as a result, the linear fluorescence probes with high sensitivity that using for the fast and precision recognition and quantitative detections of pesticide residues and other environmental pollutants can be obtained.

芳香多羧酸稀土配合物作为一种重要的功能发光材料，兼具稀土和多羧酸配体的优点，在光学材料、荧光传感及生物识别等领域展现出了巨大的应用前景。本项目拟围绕芳香多羧酸稀土基荧光材料这一研究热点，以线性荧光探针性能为导向，设计合成具有特定对称性和配位官能团的芳香多羧酸配体，与稀土簇构筑稀土配合物，对其结构组成和空间构型进行准确确定；探索反应中各种因素对最终产物结构的影响，研究该类化合物的形成条件及结构特征和规律，为芳香类多羧酸稀土簇基配合物的可控制备提供理论依据。通过引入不同的金属离子和调节掺杂金属的比例来调控目标产物的发光性能，考察其作为线性荧光探针对农药残留等环境污染物的识别和定量检测的性能，阐明其识别机理。本项目旨在设计特定节点的芳香多羧酸配体和不饱和位点的稀土簇，可控构筑稀土簇基发光材料，筛选出高灵敏度的芳香多羧酸稀土簇基类线性荧光探针材料，用于快速准确地识别和定量检测农药残留等环境污染物。

荧光配合物作为一种重要的功能发光材料，在光学材料、荧光传感及生物识别等领域展现出了巨大的应用前景。本项目围绕芳香多羧酸配合物这一研究热点，以荧光探针性能为导向，设计合成具有特定对称性和配位官能团的芳香多羧酸配体，与不同的金属离子反应构筑晶态多羧酸配合物，利用X-射线单晶衍射等手段对其结构组成和空间构型进行准确确定；探索反应中各种因素对最终产物结构的影响，重点探索了反应溶剂、温度和pH等因素对金属离子和羧基的配位模式的影响，对比总结所得配合物的形成条件及结构特征和规律，为芳香类多羧酸配合物的可控制备提供了理论依据。利用X-射线粉末衍射、热分析、红外光谱等对所得化合物的固态及其在溶液中的稳定性进行了研究。考察了所制得的配合物的发光性能，特别是作为荧光探针对环境污染物的识别与检测性能，包括重金属离子、阴离子、硝基芳香化合物和农药等环境污染物。结合配体及目标产物的电子结构与光谱性质，对其识别机理进行深入分析研究。此外，对所得到的部分配合物的磁性和催化也进行了初步研究。本项目研究过程中，发表标注该基金资助号的SCI论文9篇，获中国授权发明专利1项。