有机硅功能化亚胺衍生物的合成及在配合物材料中的应用

In order to fill the research blank of the analysis of the structures and the properties of the metal complexes functionalized with the organosilicon groups, this research project will mainly focus on the synthesis of new imine derivatives containing organosilicon groups and studies on their applications in functionalized metal complex materials. Therefore, we will functionalize the pyridine, 1,10-phenanthroline and their derivatives with some special organosilicon groups to obtain novel derivatives of imine, and then these imine derivatives will be applied to synthesize the metal complexes with Ag(I), Re(I), Cu(II), Ru(II), and Ln(III) as centre ions, respectively. And these metal complexes should have the potential applications in light-emitting materials and gas adsorption materials, and so on. At last, the relationship between the properties and the position of organosilicon groups and those of the corresponding metal complexes should be systematically studied by the characterization and the analysis of the photophysical properties (including the photoluminescent spectra, the UV-Vis absorption spectra, the excited-state decay lifetime, and the luminescence quantum yield, etc.), the electrochemical properties, the thermal stabilities, and the gas adsorption properties of the synthesized metal complexes. As a result, series of the derivatives of imine compounds with organosilicon groups would be synthesized and used to construct the novel functionalized metal complexes, which would also further enrich the category of metal complexes and their applications. 5-10 research papers indexed by SCI could be published and 3-6 postgraduates and 1-3 Ph D students would finish their research thesises if this project is financially supported by NSFC.

本项目以填补有机硅基团功能化配合物结构与性质研究的空白为研究动力,以有机硅基团功能化新型亚胺衍生物的合成及在配合物材料中的应用为研究内容，通过有机硅基团对吡啶、1,10-邻菲罗啉等亚胺衍生物进行功能化和结构化，合成出系列新型亚胺衍生物，然后与Ag(I),Re(I),Cu(II),Ru(II),Ln(III)等金属离子进行配位反应，合成新型配合物发光材料及配位聚合物气体吸附材料，通过对目标配合物材料的光物理性质(荧光光谱性质，激发态衰减寿命和发光效率等)、电化学性质、热稳定性及气体吸附性质的分析与表征，最终实现探索有机硅基团的结构与位置对功能化配合物的结构与性质的响影规律的研究目标。因此实施本项目在开发有机硅基团功能化的亚胺衍生物和相应配合物功能材料的同时，将进一步丰富配合物种类、拓展配合物材料研究范围。实施本项目将发表5-10 篇SCI检索论文,培养3-6名硕士研究生和1-3名博士研究生。

在本项目的资助下，主要开展了以下几方面工作:1)合成的8种新型有机硅功能化二亚胺衍生物。实验研究表明，通过在其THF溶液加入不同比例的水、乙醇、乙腈、三氟乙酸或乙酸时，光致发光光谱性质可以发生明显变化，这种变化初步被归为溶剂化效应。此外，以该系列二亚胺化合物为配体合成了系列ReI配合物。经研究发现这些ReI配合物具有明显的聚集诱导磷光性质；2）利用系列树枝形二亚胺化合物合成了4种CuI配合物，并对其分子结构、光物理性质和电化学性质进行了研究讨论；3）合成了两种柔性多元酸化合物，并利用这两种柔性多元酸化合物合成了9种金属配合物材料；4) 合成了3种含三唑单元的多元酸(Tz-1，Tz-2，Tz-3），并利用Tz-1和Tz-2合成了10种金属配合物材料。通过上述研究工作在Journal of Fluorescence，Journal of Coordination Chemistry，Inorganic Chemistry Communications，Journal of Luminescence等国际杂志上共发表7篇专业研究论文。培养硕士研究生8名（已经毕业3名），博士研究2名。