结合主客体发光功能的MOFs合成与薄膜材料制备研究

The synthesis of photoluminescent metal-organic frameworks (MOFs) is often dependent on the rational selection of organic ligands and metal centers, and the third important part in the MOF structure, the guest molecules or ions, is rarely considered to tune the photoluminescent properties of MOFs. This project is just to develop such kind of MOFs with photoluminescent guest molecules or ions. The method of templated synthesis will be employed to synthesize these photoluminescent MOFs and their thin film materials. Here, tetrabenzylphosphonium or tetrabenzylboron ions are chosen as the templates for the construction of related MOFs based on long aromatic ligands with carboxylate groups or pyridine groups. The detailed emission mechanism in these complex MOFs will be carefully studied. The host-guest interactions may generate unusual emission properties. Moreover, the thin films preparation and possible applications of these unique MOFs on molecular recognition and sensors will be further investigated. This project integrates the research on coordination chemistry and thin film material chemistry, and it provides multi-fold structural design strategy including tuning porous structures, charge distribution and host-guest interactions. The success on this project will lead to various novel MOFs materials with three kinds of emission parts.

发光功能导向的MOFs材料结构设计通常倾向于有机配体和金属中心的选择，而作为MOF结构重要组成部分的模板分（离）子并未受到重视。本项目着眼于含发光功能模板分（离）子的MOFs设计合成及其薄膜材料性能研究；拟选择具有发光功能的离子型模板剂（如季磷盐、芳香硼酸类离子等），利用长臂芳香多羧酸类配体或（和）长臂联吡啶类中性配体与金属离子或者二级构筑单元进行自组装，以获得各种结合主客体发光功能的微孔MOFs发光材料，同时筛选部分性能优良的MOFs发光材料，重点探索其薄膜材料制备方法以及发光MOFs材料在白光LED或荧光传感方面的功能应用。本项目结合配位化学和薄膜材料化学，涉及MOFs结构调控、电荷匹配和主客体相互作用等多重结构设计思想，将为新型具有三元发光体系的MOFs材料合成及薄膜制备奠定基础。

我们按照项目计划与目标开展了系统的研究工作。从配体、模板剂的合理选择出发，通过合成方法的设计，我们成功构筑了系列功能MOFs材料和多面体配位金属有机笼材料，探索制备了数例金属有机框架（MOFs）薄膜材料，并系统研究了系列材料在发光、三阶非线性光学与催化方面的功能应用。研究结果为相关新材料的设计合成和功能应用研究奠定了一定的理论与实验基础。在项目支持下共发表论文 12 篇，其中在IF>5.0 的杂志发表 10 篇（包括 2篇 ACS Applied Materials & Interfaces, 1 篇 Small, 2 篇 Inorganic Chemistry, 1 篇 Inorganic Chemistry Frontiers)。培养了硕士毕业生 4 名。完成了项目计划，实现了研究目标。