镁基异金属配位聚合物的构筑与性能研究

This project will focus on the systematical research of the syntheses, structures and properties of magnesium-based heterometallic coordination polymers (Mg-M-CPs). The inexpensive, non-toxic, abundant magnesium ion is selected to combine with the second metal ions such as In3+, Zn2+ and Eu3+, to construct Mg-M-CPs via the linkage of multifunctional conjugated organic ligands under soft chemical synthetic conditions. The syntheses, structures and luminescent properties of Mg-M-CPs, as well as the various factors that affect the structures, stabilities, and fluorescence properties of Mg-M-CPs and the structure-property relationship will be studied systematically. Hopefully the compounds with excellent luminescent properties and fluorescent sensing properties and the applications of such compounds as precursors for the preparation of MgO-based luminescent nanomaterials will be realized. In our previous studies, we have obtained several series of heterometallic coordination polymers based on bi-metal Mg-Co, Mg-Ni, Mg-Zn and tri-metal Mg-Li-Co, and found that introducing dissimilar metals can improve the stabilities and enhance the intensities of fluorescent emission of the resulting Mg-M-CPs. The project will not only enrich the structural types of CPs and promote the research on designable synthesis of functional heterometallic CPs, but also provide a new route towards the use of rich magnesium resource in china; thus it has important scientific significance.

本项目拟开展镁基异金属配位聚合物（Mg-M-CPs）的合成、结构与性能的研究。选择无毒、价廉、丰度高的Mg2+离子同In3+、Zn2+、Eu3+等离子组合，在软化学合成条件下，和含特定功能团的共轭有机配体组装构筑Mg-M-CPs；系统研究其合成、结构和荧光性质，考查异金属组合等各种因素对化合物结构、稳定性和荧光性能的影响规律；探讨构效关系；以期获得稳定性高、荧光性能好的Mg-M-CPs，开发其在光致发光、荧光检测以及做为前驱体制备纳米氧化镁发光材料等方面的应用。申请人的前期工作已成功构筑了Mg-Co、Mg-Ni、Mg-Zn等二元、Mg-Li-Co等三元系列Mg-M-CPs，并发现异金属组分的引入有助于提升镁基化合物的稳定性和荧光性能。本研究不仅能够丰富配位聚合物的结构类型，为异金属功能配位聚合物的设计合成提供借鉴，而且将为中国丰富的镁资源的利用提供一条新途径，具有重要的科学意义。

本项目提出将无毒、价廉、丰度高的Mg2+离子同In3+、Zn2+、Eu3+等离子组合，在软化学合成条件下，和含特定功能团的共轭有机配体组装构筑Mg-M-CPs，考查异金属组合等各种因素对化合物结构、稳定性和荧光性能的影响，开发其在光致发光、荧光检测等方面的应用。在溶剂热条件下，合成了若干系列结构新颖的Mg-Zn、Mg-CuI异金属荧光CPs，重点对其结构及荧光进行了系统的研究。其中化合物[Mg2Zn2(OH)2(1,4-NDC)3(H2O)2]∙6H2O对低浓度的CS2、Fe3+及硝基高爆物分子展现出灵敏的荧光淬灭响应；[MgZn(1,4-NDC)2(DMF)2具有力致荧光响应的行为，在外力作用下可以从绿光转变为蓝光发射；通过后合成修饰，将CuI引入到Mg2(1,4-NDC)2(H2O)2](bpy)(H2O)4三维骨架中构建双发射且可调控荧光的Mg-CuI异金属CP。该项目不仅拓展了镁金属的应用领域，丰富了配聚物的结构类型，同时为寻找性能优异的多元金属荧光配聚物提供了新的设计思路。项目研究期间，发表SCI论文10篇，其中6篇影响因子大于4；发表会议论文1篇；申请国内发明专利1项。参加项目研究的博士生毕业2名。