新型发光杂金属-有机超分子对二氧化硫及其衍生物的荧光传感研究

Sulfur dioxide (SO2) and its derivatives (sulfite and bisulfite) have been recognized as a serious environmental pollutant and once they are in excess in human body that can cause respiratory diseases. Although there are many conventional methods to detect SO2 and its derivatives, their intrinsic difficulties (e.g., complex operation, high equipment costs, long response times, etc.) often limit their practical applications. Compared with these methods, the fluorescence-based method is more attractive because of its simple operation, high sensitivity, and real-time response. At present, the key to restricting development of fluorescence-based method is to prepare materials for the fluorescence response of SO2 and its derivatives. Therefore, it is extremely important to explore materials that could efficiently and sensitively detect SO2 and its derivatives with significant fluorescence response. This project aims to use the metal-metal bond M'-M' (M = Pt, Pd) as the site of chemical action with SO2 and its derivatives, the single metal center M(M = Fe, Ru, Ir, Cu, Pt, Eu, Nd) and organic-ligands L as fluorescent response component, and then use the programmable and controlled method to synthesize the heterometal-organic supramolecule as the sensor for detecting SO2 and its derivatives. The theoretical calculations are used to establish structural models, predict intermediates, and clarify the process and mechanism. The implementation of this project will provide experimental and theoretical guidance for the efficient and sensitively detecting of materials preparation and analytical methods for SO2 and its derivatives, and provide a new reference for the design and optimization of functional materials on the environmental analysis and purification.

二氧化硫(SO2)及其衍生物是一类严重的环境污染物，当人体过量摄入能引发各种疾病。传统SO2检测操作复杂、成本高、响应慢，基于荧光的检测灵敏度高、操作简单、响应快从而成为备受关注的研究领域之一。制约其发展的关键：针对SO2及其衍生物具有荧光响应性的材料制备较难。因此探索高效、高选择性、高灵敏检测SO2及其衍生物且具有明显荧光响应的传感材料极为重要。本项目拟利用金属-金属键M'-M'(M'=Pt，Pd)为SO2及其衍生物活性作用位点，单金属M(M=Fe，Ru，Ir，Cu，Pt，Eu，Nd)与有机配体为荧光响应组分，采用程序法可控制备杂金属-有机超分子作为检测SO2及其衍生物的传感材料。运用理论计算建立结构模型，预测中间体，明确传感过程及机理。本项目的开展将为高效、高选择性灵敏检测SO2及其衍生物的材料制备和分析方法研究提供实验与理论指导，进而为环境分析与净化功用材料的设计和优化提供新的借鉴。

青年基金项目“新型发光杂金属-有机超分子对二氧化硫及其衍生物的荧光传感研究”（21906002）是2019年经国家自然科学基金委员会批准立项，2020年1月开始执行，为期3年。根据研究计划书，本项目已经基本完成了预期目标。三年来，针对二氧化硫及其衍生物等的离子识别与传感这一科学研究问题，运用超分子金属-有机配位原理，利用组装与解组装策略，发展了系列金属-有机超分子传感体系对不同离子识别的新策略和新方法，实现了包括重金属汞离子、卤素离子、磷酸根离子、二氧化硫及其衍生物等在内的若干不同离子的高效、专一选择性的识别，发现了一些影响金属-有机超分子识别选择性效率的因素与规律，探讨了识别和传感的过程和详细机理，取得了部分有特色的研究成果。项目执行三年以来，已在包括Analytica Chimica Acta，Cryst. Growth Des.，CrystEngComm，International Journal of Molecular Sciences等在内的重要国际期刊发表论文10篇，授权国内发明专利1项。在项目执行过程中，负责人获得北京市教委面上项目资助，已独立培养（毕业）硕士研究生1名和在读硕士研究生4名。