发光性能导向的稀土簇基金属-有机骨架材料的组装及调控

As a promising inorganic-organic hybrid luminous material, luminescent metal-organic frameworks (MOFs) materials have attracted extensive attention by their diverse applications in lighting, display, imaging and fluorescence sensor due to their various luminescent emissive sources, wide wavelength range, adjustable porosity and easily multifunctional modification. However, it is still a challenge for low nuclear MOF materials to achieve a satisfactory perform as fluorescence sensors because of its drawback, such as the poor stability of frameworks, the poor recognition ability in fluorescence detection and the deficiency to tune luminescent color. In this project, Luminescence directed cluster-based lanthanide MOFs materials will be assembled by selecting the organic linkers with the unsaturated coordination sites via a molecular design and assembly strategy. And the relationship of structure and property will be investigated. By introducing different solvent guests in the pore, generating nanocrystallinzed MOFs materials and sensitizing MOFs materials with other metal ions (transition metal ions or lanthanide metal ions), MOFs materials will be well tuned with the controllable luminescent properties. As a result, a fluorescence sensor with high stability and highly selective recognition ability will be employed to detect heavy metal pollutants (Cd2+、Zn2+、Cu2+、Pb2+、Hg2+) and organic pollutants from persistent pesticide of the Poyang ecological environment fast and accurately.

发光金属-有机框架材料(Luminescent MOFs)是一种新型的无机有机杂化发光材料，具有发光位点丰富、发光波长范围广、孔道尺寸和结构可调、易于多功能修饰等优点，因而在照明、显示、成像、荧光探测等领域具有广泛的应用前景。针对低核MOFs材料存在的框架稳定性差、荧光识别靶向性差及发光颜色可调控性差等问题，本项目采用分子设计与组装方法，以发光性能为导向，设计具有不饱和位点的桥联配体，构筑稀土簇基MOFs材料,并探索其结构与性能的关系。通过改变MOFs孔道中的客体分子以实现其发光性能的调控；通过将MOFs材料纳米化，研究纳米MOFs材料形貌与大小等因素对其发光性能的影响；通过引入不同金属离子来敏化MOFs材料，以此来调控MOFs材料的发光性能。筛选出具有高稳定性、特定荧光识别能力的荧光传感材料，以期获得可以快速准确地检测鄱阳流域生态环境中重金属污染及有机污染物的一类传感材料。

为了发展出对阴离子和有机小分子等污染物进行高效荧光法检测的体系，本项目合成了一系列金属-有机骨架(MOFs)材料，实现了对Cr2O72-/CrO42-，PO43-等阴离子和乙酰丙酮，苯胺等有机小分子选择性地荧光检测，并阐明了MOFs材料的结构与识别性能之间的关系，从而为设计合成具有新型结构、性能优异的簇基MOFs荧光探针材料及相关阴离子和有机小分子等污染物的检测提供了新思路和新途径。本项目顺利完成了申请书中提交的研究计划，并在Dalton Transactions，Crystal Growth & Design， Dyes and Pigments等刊物上发表标注本基金项目资助的论文19篇，申报国家发明专利8项。本项目取得的研究成果概述如下：项目以配位化学基本原理为指导，围绕“具有荧光性能的稳定MOFs材料的合成、表征与荧光检测应用”开展工作，设计合成了系列具有荧光发射性能的簇基Eu(III)/Tb(III)、Zn(II)及Zn(II)-Eu(III)/Zn(II)-Tb(III) MOFs材料，并可选择性、灵敏性、有效地荧光识别Cr2O72-/CrO42-，PO43-等阴离子和乙酰丙酮，苯胺等有机小分子。本项目阐明了MOFs材料的组成、结构与分析物性能之间的关系，阐明了MOFs材料选择性识别阴离子和有机小分子等污染物的机理，为进一步合成稳定簇基MOFs材料及荧光传感应用提供了新的思路和研究基础。