自旋交叉荧光金属有机框架化合物的合成及其在分子检测中的应用

Spin crossover (SCO) materials, in which high-spin (HS) and low-spin (LS) states can be interconverted by the absorption and desorption of guest molecules, have potential applications in future technologies molecular sensing devices. In this project, I aim to combine the porosity, fluorescence and spin-crossover behaivour in one material, and investigate the synergetic influence of the guest molecules on the fluorescence and spin-crossover hehaviour and improve the sensing performance of the complexes. The main research includes the following aspects: 1) Design and syntheses of organic bridging ligands with strong fluorescence with BODIPY fluorescent functional group. 2) Preparation of porous three-dimensional Hoffman-type metal-organic frameworks showing fluorescent and spin-crossover properties by combining the fluorescent ligand, FeII ions and [MII(CN)4]2− (M = Ni, Pd or Pt) metallocyanide ions, and characterization of the crystal structures, fluorescent properties and magnetic susceptibilities at various temperatures. 3) Investigation of the influence of guest molecule absorption on the crystal structures, fluorescent properties and spin-crossover properties for the complexes. Discuss the relations between the host-guest interactions, fluorescent properties and spin-crossover properties, and improve the sensing performance of the complexes.

自旋交叉化合物的电子构型可随客体分子的吸附/解附发生可逆转变，使其在分子识别、分子传感器的开发等方面具有广阔的应用前景。本项目旨在将多孔性、荧光和自旋交叉三种性质复合到一种材料中，并研究客体分子对自旋交叉行为和荧光性质的协同性相互作用，优化化合物对分子检测的性能，实现多信号输出的智能响应材料。申请人将在以下几方面开展工作：1）以BODIPY荧光基团作为母体，设计合成具有强荧光特性的双齿桥连配体；2）将该荧光有机配体与FeII离子和[MII(CN)4]2−（M = Ni、Pd或Pt）金属氰根阴离子反应，合成具有荧光性质和自旋交叉行为的三维双金属霍夫曼型框架化合物，并表征其变温结构、荧光性质、变温磁化率；3）比较研究吸附客体分子前后化合物的结构、荧光和磁性变化，揭示主客体相互作用、自旋交叉和荧光性质三者之间的内在联系，实现多信号输出的智能响应材料。

自旋交叉化合物作为一种具有分子双稳态特性的分子基磁性材料。金属有机框架是具有周期性无限延展结构的多孔晶态材料。本项目合成了多个具有自旋交叉行为的单核或四核配位化合物，通过测试其在不同温度下的单晶结构和磁性数据，分析构效关系，进一步分析了客体分子与它们的分子间相互作用对其双稳态行为的影响；合成了基于BODIPY荧光基团的桥连配体，并通过金属离子将其连接成金属有机框架；通过粉末X-射线衍射、氮气吸附、红外光谱、固体核磁共振光谱、高分辨透射电镜等分析了多个二维金属有机框架材料的结构，并研究了它们对苯乙炔类分子的特效催化反应。