表面化学反应构筑稳定自组装纳米结构的研究

Orderly atomic and molecular assembly on the surface is a powerful tool for preparing functional nano-systems. By controlling the shape of the formation and composition of surface structure, a wide range of self-assemble surface nanostructures can be obtained. In recent years, directly synthetic ordered covalent organic aggregates and network structure on the surface has attracted wide attention. On the surface of solid substrate, the covalent bond organic nanostructures were obtained by metal-surface catalysis and solvent induced. Although zero-dimensional and one-dimensional chain assembly or rod-like structure can be performed without topological defects on the surface, however, there are many structural limitations to achieve long-term covalent interconnected ordered two-dimensional organic network. This project intends to build surface nanostructures on insulated and non-insulated substrates by selecting a variety of molecular nanostructures, types of functional groups, the environment and conditions; then solve the issues when preparing the nanostructures by the covalent bond on the view of the surface chemical reactions. Moreover, applying the surface structure of various molecules for molecular recognition, self-assembly and reaction. It is important to study single molecules, intermolecular interactions between the molecules and the substrate and development of the theory to achieve self-assembled surface for regulation of surface nanostructures.

规整表面上的有序原子和分子组装是制备功能性纳米体系的有效途径。通过控制表面结构的形状和组分，可以自组装得到大范围的表面纳米结构。近年来，直接在表面上构筑有序的有机共价键纳米结构引起了广泛关注。在固体衬底上，利用金属表面催化，或者溶剂作用诱导共价键连接构筑表面有机纳米结构。尽管，零维组装体、一维链状或棒状结构在表面没有任何拓扑缺陷。但是，实现长程有序的二维共价键相互连接的有机网络目前还有很多结构的限制。本项目选择绝缘和非绝缘两类衬底，通过改变有机分子结构、官能团类型、反应条件，研究表面化学反应机理。并且，在表面制备多种分子纳米结构以用于分子识别、组装和反应。本项目的开展将对研究单分子、分子间、分子与基底的相互作用，掌握表面化学反应，发展表面自组装理论并实现对表面纳米结构的调控具有重要意义。

近年来，直接在表面上构筑有机化学反应引起了广泛关注。利用本实验室在分子自组装方面的坚实基础以及SPM技术上的优势，本项目集中研究以下几方面内容：1）借助STM研究了在表面通过shiff-base反应形成的共价有机网格（COF）；2）首次探究了在液-固、气-固两种界面发生Knoevenagel反应的情况，记录了碳碳双键的形成过程，并进行了傅立叶变换红外（ATR / FT-IR）和紫外可见吸收等表征；3）利用扫描隧道显微镜（STM）研究了大气条件下锌酞菁与1，3-二（4-吡啶基）丙烷在2,6,11-三羧基癸氧基-3,7，10-三十一烷氧基三亚苯（不对称TTT）分子模板中的配位过程；4）在固/液界面合成了苯并噻唑衍生物的自组装单分子层。这些研究不仅扩展了表面反应的范畴而且也能应用到在表面设计多功能自组装单层。