微孔荧光金属有机骨架化合物构建及其对客体变色响应研究

Presently, the current focus of research concerning the metal organic frameworks is on the adsorption effect of gas molecules, such as N2, H2, etc, and thus the application of these materials is limited by the situation.Introducing the guest molecules into the cavities of porous metal organic frameworks causes the fluorescent properties (including wavelength and intensity) of the framework to change, resulting in the discoloration effect.This kind of material with an effect of fluorescence, based on metal organic frameworks, is of potential significance applied in the molecule sensor field. The relevant research is still in its infancy. Meanwhile, the compound based on the porous metal organic frameworks with fluorescent and discoloration effect to guest molecules are rarely reported. Thus, constructing and studying these materials are of importance and necessity. This project based on luminescent organic linkers coordinated to metal ions, is aimed at constructing porous metal organic frameworks.Introducing the luminescent organic linkers into the frameworks makes it possible for the material to have luminescence and porosity simultaneously. The project,in order to reveal the synthesis law and relationship between structure and property, discover and set up synthesis methods for molecular functional materials, and deep apprehend the physical essence of the relationship between structure and property of the materials, is required to do research on designing, synthesis and the relationship between structure and property, as well as the luminescent discoloration effect along with its underlying causes.

当前对金属有机骨架化合物的研究主要集中在对氮气、氢气等气体分子的吸附上，这限制了这类材料的应用。而对客体有着荧光变色响应的微孔金属有机骨架化合物鲜有报道，相关研究还处于起步阶段。本项目拟利用有着荧光性质的两性离子有机连接体同金属离子配位，构筑微孔金属有机骨架化合物。通过将荧光有机配体引入骨架，使得构筑的化合物骨架同时有着微孔和荧光性质。客体分子进入到微孔金属有机骨架化合物空腔中时，骨架的荧光性质，如波长、强度可能会发生改变，产生变色响应。所构建的材料在分子传感领域有着重要的潜在应用价值，拓宽了金属有机骨架化合物的应用范围。通过研究这类功能配位骨架化合物的设计、合成、结构调变与材料性能的关系、对客体荧光变色响应及内在原因，从而揭示这类材料的合成规律及结构与性能的关系，探索和建立分子基功能材料的合成和制备方法，深入认识材料构效关系的物理本质。

金属有机骨架化合物是一类重要的有机无机复合材料，其在气体吸附、催化、非线性光学等领域有着重要潜在应用。目前如何构筑这类材料仍是一项极具挑战性的工作。本课题拟基于两性离子有机物，构筑微孔金属有机骨架化合物，调控金属有机骨架结构，研究化合物对客体分子的荧光溶致变色效应，从而拓宽金属有机骨架化合物的应用范围，探索和建立分子基功能材料的合成和制备方法，深入认识材料构效关系的物理本质。.在项目执行过程中，我们发现吡啶盐两性离子衍生物对金属有机骨架结构形成具有诱导效应，是一类全新的结构诱导剂，为了同模板剂，结构指向剂（SDAs）相区别，我们提出了结构诱导剂（SIAs）的概念。我们发现一例二维金属有机笼合物，该笼合物对二氯甲烷、三氯甲烷具有荧光增强溶致变色效应，这在以前的文献中未见报道。.到目前为止，在本项目支持下，已经在Inorg. Chem., J. Coord. Chem., New J. Chem., J. Am. Chem. Soc., Sci. Adv., Dyes Pigm., Nanoscale 等期刊上共发表SCI论文21篇，其中项目主持人为第一通讯人6篇，另有1篇刚被J. Coord. Chem.接收（项目主持人为第一通讯人）。项目执行期间，主持人前往安徽大学进行博士后工作，同安徽大学合作人联合指导培养研究生三名。