萘二酰亚胺基纳米多孔材料的合成与光电应用

In recent years, naphthalene diimide (NDI) fluorescent dyes have drawn widespread attention due to their outstanding photophysical properties and high photostability. In this project, we will use core-substituted naphthalene diimides (cNDIs) as the basic building blocks to synthesize a series of metal-organic framework (MOF) and covalent organic framework (COF) film materials. In thia-aza crown ether, thiourea group substituted cNDIs constructed MOF and COF film materials, we mainly study their high sensitivity and visualization in detecting heavy metal ions (such as mercury ions). In alkyl amines, thienyl and cyano group substituted cNDIs based MOF and COF film materials, we will systematically study relationship between their electrical conductivity performance and their porous structure, cNDIs electronic properties, host-guest interaction, which will build up scientific foundation for the design and synthesis of conducting porous material at the molecular level.

近年来，萘二酰亚胺（NDI）类荧光染料因其良好的光物理性质和较高的光稳定性而广受关注。本项目拟研究以母体核心取代的萘二酰亚胺（core-substituted naphthalenediimides,cNDIs）为基本构筑单元合成一系列金属有机框架（metal organic frameworks,MOFs)和共价有机框架 (covalent organic frameworks,COFs)薄膜材料及其应用。基于硫氮杂冠醚、硫脲基团的cNDIs构筑MOFs、COFs薄膜材料并应用于重金属离子的高灵敏度可视化识别。基于烷基胺、噻吩基和氰基基团的cNDIs构筑MOFs、COFs薄膜材料，通过系统的电子导电性能评价，建立薄膜材料导电性能与其孔道结构、cNDIs结构单元电学性质以及主客体作用的对应关系，从而达到在分子层面上控制材料的导电性能，奠定导电多孔材料设计合成的科学基础。

近年来，萘酰亚胺、吩嗪、吡咯、四硫富瓦烯等功能基团因其具有可调控的氧化还原状态而受光电功能材料界研究人员广泛关注。本项目主要研究母核取代萘酰亚胺、吩嗪等为光电活性单元构筑的新型多孔骨架材料包括金属有机框架(metal organic frameworks, MOFs)、共价有机框架(covalent organic frameworks, COFs)的合成、成膜及其应用。与传统的萘酰亚胺基单体相比，母核取代萘酰亚胺基多孔材料由于其单体有较好的溶解性，由此制得的聚合物薄膜致密均匀，薄膜材料具有更稳定的电致变色性能。通过Buchwald-Hartwig偶联反应，成功地将富有电子的吩嗪单元嫁接到多孔聚合物材料中。吩嗪基多孔聚合物氧化后所得的自由基阳离子在胺类氧化偶联反应中催化性能优异，而且其可以被循环利用。此外，将光活性染料封装在金属有机框架材料中，借助其氧化还原状态的可调控性，制得的复合材料可用于荧光选择性识别尼古丁等生物标记物分子。