基于聚集诱导发光配体金属有机骨架多孔材料的组装及传感性能研究

This project aimed to use emission enhancement of aggregation-induced emission (AIE) organic compounds in solid-state and introduce AIE effect into porous coordination complexes, and thus obtained porous metal organic framework sensing materials with fluorescence signal transduction. Pyridine and carboxylic acid coordination groups were grafted into tetraphenylethylene (TPE) and 9,10-distyrylanthracene (DSA), through which we obtained a series of AIE organic bridge ligands. Porous metal organic complexes were synthesized by reaction these ligands with metal ions, and the relationships between the torsion angles of AIE organic ligands’ double bonds, and the dihedral angles of the double bond and the aromatic ring planes, and electronic transition energy barrier were explored. Furthermore, the effects of energy barrier and energy transfer pathway on the luminous efficiency were studied. In the end, The weak force of π-π and C-H…π, electron effect and vapor pressure of nitro organic compounds, soft and hardness of cationic Lewis acids and bases, and symmetries and sizes of anions between luminescent metal organic framework porous materials and guest molecules, were explored, and thus high efficient luminescent metal organic framework sensors were screened out. These related researches played an important role in the development of coordination chemistry, supramolecular science, organic chemistry and photochemical and so on.

本项目旨在利用具有聚集诱导发光(AIE)效应有机化合物在固态发光效率增强这一特点，将这一效应引入到金属有机多孔配合物中，获得荧光信号转导多孔金属有机骨架传感材料。项目通过在四苯乙烯(TPE)和9,10-二苯乙烯基蒽(DSA)上嫁接吡啶或羧酸配位基团，获得一系列AIE有机桥连配体，这些配体与金属离子配位组装形成多孔金属有机骨架。探索金属有机骨架中AIE有机配体双键的扭角、双键和芳香环平面间二面角等与配体电子跃迁能垒之间的关系，进一步考察能垒、能量转移途径对发光效率的影响。最终，研究主体与客体有机分子间π-π和C-H…π弱作用力、硝基有机物电子效应和蒸气压、阳离子Lewis酸碱软硬度和阴离子对称性和大小等因素对发光金属有机骨架多孔材料传感性能的影响，筛选出对身体和生命有毒害的离子和有机化合物的高效发光金属有机骨架传感器。此项目的研究对发展配位化学、超分子科学、有机化学和光化学等领域有重要的意义。

聚集诱导发光化合物在聚集态或固态下，它们分子的旋转受到了限制，因而发光强度比在溶液里强很多倍。而将四苯乙烯和9,10-二苯乙烯基蒽引入到金属有机骨架配合物的主体上，可以减少由于分子转动和振动导致的非辐射弛豫，提高聚集诱导发光类有机配体的发光效率（晶体诱导发光增强，CIEE），获得高强度发光的金属有机骨架多孔配合物，它们在传感性能研究时，可以通过“裸眼”观察，达到可视化的效果。本项目旨在通过在聚集诱导发光有机化合物四苯乙烯和9,10二苯乙烯基蒽上嫁接配位基团，设计合成了10多个聚集诱导发光有机桥连配体。通过单一配体、混合配体和金属离子配位，金属有机骨架封装合成，获得三十多个聚集诱导发光配体强发光配合物，成功得将四苯乙烯等聚集诱导发光基团引入到金属有机骨架材料中。这些四苯乙烯基金属有机骨架配合物都具有强的发光性能，发光金属有机骨架最高的固体绝对荧光量子产率达到99%，并且对挥发性有机物，抗生素，农药，糖类化合物及氨基酸具有传感性能，检测限达到ppm级。通过研究总结多个四苯乙烯和9,10-二苯乙烯基蒽衍生物聚集诱导发光配体金属有机骨架的配位组装行为，创建了聚集诱导发光性能配体金属有机骨架多孔配合物的有效合成方法。 基于这些发光金属有机骨架多孔配合物中四苯乙烯和9,10-二苯乙烯基蒽衍生物结构与配合物发光效率之间的影响规律，建立了配合物结构与发光性能之间的构-效关系，实现发光性能的优化和调控。同时对这些发光金属有机骨架进行了传感性能研究，总结经验规律，甄选出了高效的金属有机骨架多孔配合物传感材料，项目部分研究成果在包括ACS Appl. Mater. Interfaces，Chem. Commun.,和J. Mater. Chem. C杂志上发表6篇SCI论文(5 篇中科院一区)，以及申请了2项专利。相关的研究对发展配位化学、超分子化学、有机化学和光化学等领域有重要的研究意义。