单晶-单晶拓扑光化学合成制备功能可调的新型高分子材料

项目名称： 单晶-单晶拓扑光化学合成制备功能可调的新型高分子材料

项目编号： No.21471125

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 杨士烑

作者单位： 厦门大学

项目金额： 85万元

中文摘要： 以合适的金属离子和可发生光化学反应的有机配体和客体分子组装多孔金属-有机框架做为分子反应器，同时将客体分子嵌入分子反应器的孔隙中，进而通过光激发发生固相拓扑化学反应，将发生三类光化学反应，即配体之间、配体和客体之间，以及客体分子之间通过头对尾[2+2]光加成聚合反应。在多孔金属-有机框架孔隙的空间控制效应下，这些拓扑化学聚合反应将产生组分可变、立构规整、功能可调的高分子产物。将通过逐步引发反应，在时间上控制三个拓扑化学聚合反应（并伴随着三个独立的异构化反应）。其反应的机理将通过逐步的单晶X-射线衍射进行研究，以获得立体化学效应的快照。将详细探讨拓扑化学合成所获得的高分子产物的性质，以及它们在染料敏化太阳能电池方面应用。

中文关键词： 无机合成；晶体结构；功能材料；多孔材料；金属有机骨架

英文摘要： Molecular reactors based on porous metal-organic frameworks (MOF), will be synthesized from a combination of appropriate metal ions, photoreactive ligands and guest molecules. Guest molecules will be incorporated into the MOF cavities (Molecular Reactors). Subsequently, photo-initiated topochemical reactions will be carried out. Three distinct types of photoreactions, viz., between guest molecules, between guest molecules and ligands, and between ligands via head-to-tail [2 + 2] additions will occur. These topophotochemical polymerization reactions produce component-tailorable, stereoregular, and function-adjustable polymers in the spatially controlled MOF cavities. Temporal control is achieved by a stepwise triggering of the three topophotochemical polymerization reactions (along with three separate isomerization equilibria). The kinetics of these photoreactions will be explored by varying the UV wavelengths. The mechanism will be monitored in a step-by-step manner by single-crystal X-ray diffraction, producing a snapshot picture of the stereochemical effects. The properties of the polymers obtained in the topophotochemical syntheses will be studied in detail. The application of these polymers as dye-sensitized solar (DSSC) cell materials will be explored.

英文关键词： Inorganic synthesis;Crystal structure;Functional material;Porous material;Metal-organic framework