表面交叉偶联反应的研究

近年来表面有机反应的兴起与发展，开辟了一个有别于传统有机合成化学的新型研究领域，为化学合成的精准化提供了新的途径。交叉偶联反应要求两种有机反应物都不发生自身偶联反应，而是选择性地发生彼此间的偶联反应。在表面实现交叉偶联反应将为在分子水平“自下而上”地精准构建有机功能材料提供方法和手段，是亟待解决的前沿课题。本项目拟利用过渡金属基底的催化（活化）性能，从反应物分子的设计与合成出发，通过表面限域效应抑制有机反应物的自身偶联反应，在分子水平发展出一系列选择性的新型表面交叉偶联反应。并将以高分辨扫描隧道显微镜和二次离子质谱为主要表征手段，结合理论计算，对反应过程与机理进行深入研究。在此基础上，进一步在分子水平发展出一维、二维共轭聚合物材料的合成方法。本项目的完成将为带有各种不同功能基团的有机单体分子的表面交叉偶联反应提供模型反应，并为宏观尺寸的新型功能材料和界面材料的精准可控制备奠定基础。

The recent emerging and progress of on-surface synthesis have opened a new field besides the traditional organic synthetic chemistry, and provided a new way of precise synthesis. The cross-coupling reactions require that two reactants do not undergo the homo-coupling reaction, but selectively couple with each other. It is an urgent topic to realize such reactions on surface because they would provide protocols for the "bottom-up" construction of organic functional materials in molecular level. This project plans to utilize the catalytic (activation) ability of the transition-metal substrates, and inhibit the homo-coupling reaction through the surface-confinement effect and proper design and synthesis of organic reactant molecules. Then, a series of novel and selective cross-coupling reactions on surface might be achieved in molecular level. Using the high-resolution scanning tunneling microscopy and secondary ion mass spectrometry as the characterization tools, and in combination with calculation, the reaction process and mechanism would be investigated thoroughly. On this basis, the further synthesis of one-dimensional and two-dimensional conjugated polymer materials might be achieved in the molecular level. The completion of this project would provide model reactions for the on-surface cross-coupling of a variety of organic monomers containing different functional groups, and lay a foundation for the precise preparation of functional materials and interfacial materials in macro scale.