芘基金属有机框架的合成及其对苯衍生物的荧光传感

Benzene and its derivatives such as toluene, ethylbenzene, xylene, chlorobenzene, are common pollutants in daily life and greatly harmful to our health. As no special functional groups in the structures, showing chemical inertness, detecting them is really difficult. In this project, we are to design and synthesize three kinds of novel pyrene-based ligands, and use for constructing porous fluorescent metal-organic frameworks (MOFs) further. By adopting reasonable mix-ligands strategy, we design to synthesize interpenetration structure, and introduce pyrene excimers into MOF by partial overlapping of pyrene moieties. Computational simulation confirmed the hypothesis. When benzene and its derivatives are uptaken into MOF channels, the difference among their molecule sizes leads to the change of degree of pyrene overlap, causing relevant fluorescence response. Meanwhile, we are also to investigate the detection limit and recyclability of MOF sensors. Sensors with excellent detection performance are to be made into device for direct applications in daily life and industrial production. Pyrene excimer based fluorescence sensors provide a new opportunity for designing fluorescent sensors, and detecting benzene and its derivatives offers a new sight in pollutant treatment and environmental protection.

苯及其衍生物如甲苯、乙苯、二甲苯、氯苯等都是日常生活中常见的污染物，对人的身体危害极大。这类物质结构中没有特殊官能团，化学性质又相对惰性，因此对它们进行检测十分困难。本项目拟设计合成三种基于芘的配体，用于构筑多孔荧光金属有机框架(MOFs)材料。通过采用合理的混配体策略，设计合成出贯穿的结构，通过芘官能团的部分重叠从而将芘激基缔合物引入到骨架中，同时结构模拟的结果证实了其可行性。当苯及其衍生物被吸附进MOFs的孔道中，依据其三维分子尺寸的差异造成的芘激基缔合物中芘重叠程度的变化，产生相应的荧光响应，从而实现特定性传感。同时，还将对MOFs荧光传感器的检测限以及可循环性进行研究，对于检测性能优异的材料还将被制成器件，直接应用于日常生活以及工业生产中。这类基于芘激基缔合物的荧光传感器不仅为荧光传感器的设计提供新的契机；而且其对苯及其衍生物的荧光传感也为污染物处理和环境保护提供了一个新的视角。

苯及其衍生物如甲苯、乙苯、二甲苯、氯苯等都是日常生活中常见的污染物，对人的身体危害极大。这类物质结构中没有特殊官能团，而且化学性质又相对惰性，因此对它们进行检测十分困难。本项目通过设计合成新型具有荧光特性的金属有机框架（MOFs）材料，以CuI为金属源，利用铜碘簇的荧光特性，成功合成出一系列荧光MOF。通过调控结构中阳离子有机胺的种类，从而实现对系列MOF的孔道调控，从而实现对荧光的调节；同时我们还进一步通过调节有机配体的组成，利用含不同官能团的吡嗪配体与CuI反应，成功得到一系列荧光MOF材料，其荧光发射可以从红光到橙光到黄光再到绿光，实现连接调控，其Stokes位移可达接近100nm。这些荧光材料合成方便，有望将其商品化并应用于分子识别领域。