【作者】 刘子玲；

【导师】 陈龙； 张文勤；

【作者基本信息】 天津大学 ， 化学， 2022， 硕士

【摘要】 共价有机框架（Covalent Organic Frameworks,COFs）是一类具有周期性骨架,有序的纳米多孔结构,可兼容功能性有机单元的结晶性多孔聚合物。COFs的可预先设计性原理与线性聚合物、超支化聚合物、交联聚合物和生物聚合物不同,它能够利用拓扑结构定向引导构筑单体的相对位置,为构筑理想的COFs提供了先导条件。对于COFs的设计与合成,除了可以直接通过自下而上的方式对其进行结构设计合成外,也可以对现有的COFs进行后修饰,丰富COFs的结构多样性。作为新型多孔材料,不同的COFs因具有不同的内核,孔径大小及晶体结构,使其在催化,传感,吸附,能量存储,质子传导等方面的应用前景相较其他聚合物更为广阔。本文通过引入不同内核单元构筑了三例新型COFs,并系统地研究了COFs在光催化,荧光检测及分子吸附性能。一、喹吖啶酮（QA）衍生物是一种具有高性价比的光学活性染料,其在有机发光二极管、有机太阳能电池和光催化等领域得到了广泛的研究。本文通过卤化苯与喹吖啶酮的N-芳基化反应合成了一种具有“Z”字形结构的新型缩醛保护的喹吖啶酮单体（QA-PCHO）。通过QA-PCHO与两种具有C₃对称性的氨基单体（TAPT或TAPB）的缩聚反应,我们制备了两个基于QA的介孔COFs（>4.7nm）。与未保护醛基单体（QA-CHO）合成的QA-COFs相比,QA-PCHO合成的QA-COFs结晶性更好。鉴于COFs中喹吖啶酮的密集均匀分布及特殊的光学活性,所构筑的QA-COFs不仅丰富了COFs的结构多样性,而且作为光催化剂在需氧环化波瓦罗夫反应（Povarov reaction）中呈现出优异的催化性能（较好的稳定性,良好的底物普适性和优异的官能团相容性）。另外,QA-COFs的N,N-二甲基甲酰胺（DMF）分散液具有较强的荧光,可用于选择性检测铁离子。二、全共轭的环戊基醋蒽烯（CP）具有优异的接受电子的能力,通过9,10-二溴蒽与4-[2-（4-甲酰苯基）乙炔基]苯甲醛通过交叉耦联反应合成CP-CHO,将其与对苯二胺在溶剂热条件下缩聚制备了CP-COF,其在碘吸附过程中表现出优异的性能。更多还原

【Abstract】 Covalent organic frameworks(COFs)are a class of crystalline porous polymers with periodic frameworks,ordered nanoporous structures,and compatible functional organic units.Different from linear polymers,hyperbranched polymers,cross-linked polymers and biopolymers,the design principle of COFs can precisely locate the relative positions of building monomers based on the topological orientation,which is advantageous to build the desired COFs.Besides the direct bottom-up method to syntheize COFs,the COFs can also be post-modified to enrich the structural diversity of COFs.COFs have shown promising applications in catalysis,sensing,adsorption,energy storage,and proton conductions due to their inherent porosity,tunable pore sizes and functions,etc.In this paper,three novel COFs were constructed by introducing different core units,and the performance of these COFs in the fields of photocatalysis,sensing and adsorption were systematically investigated.1.Quinacridone(QA)derivatives are cost-effective and optically active dyes,which have been extensively studied in the fields of organic light-emitting diodes,organic solar cells and photocatalysis.In this work,a novel acetal-protected quinacridone monomer(QA-PCHO)with a "Z"-shaped structure was synthesized by N-arylation of halogenated benzenes with quinacridones.By polycondensation of QAPCHO with two C3-symmetric amino monomers(TAPT or TAPB),we prepared two QA-based mesoporous COFs(>4.7 nm).Compared with the QA-COFs synthesized from the unprotected aldehyde monomer(QA-CHO),the QA-COFs prepared from QAPCHO have better crystallinity.Regarding to the configuration and optical activity of densely and uniformly distributed quinacridone in the skeletons,the QA-COFs not only enriched the structural diversity of COFs,but also served as photocatalysts in the aerobic cyclization of the Povarov reaction and exhibited excellent catalytic performance(better stability,good substrate universality and excellent functional group compatibility).In addition,the N,N-dimethylformamide(DMF)dispersions of the QAbased COFs displayed strong fluorescence,which were used for the selective detection of iron ions.2.Fully conjugated cyclopent[hi]aceanthrylene has excellent electron-accepting ability.CP-CHO was synthesized via cross-coupling of 9,10-dibromoanthracene with4-[2-(4-formylphenyl)ethynyl]benzaldehyde,which was polycondensed with pphenylenediamine to synthesize CP-COF under solvothermal conditions.CP-COF showed excellent performance in the process of iodine adsorption.更多还原