Materials Genome Institute, Shanghai University, 200444 Shanghai, China.
Phys Chem Chem Phys. 2022 Sep 21;24(36):22122-22128. doi: 10.1039/d2cp03073j.
On-surface synthesis has been a subject of intensive research during the last decade. Various chemical reactions have been developed on surfaces to prepare compounds and carbon nanostructures, most of which are centered on the carbon-carbon bond formation. Despite the vast progress so far, the diversity of functional groups in organic chemistry has been far less explored in on-surface synthesis. Herein, we study the surface-assisted synthesis of ethers through the homocoupling of hydroxymethyl substituents on Ag(111). By using two hydroxymethyl substituent functionalized molecular precursors with different symmetries, we have achieved the formation of ether chains and rings. High-resolution scanning tunneling microscopy complemented with density functional theory calculations are used to support our findings and offer mechanistic insights into the reaction. This work expands the toolbox of on-surface reactions for the bottom-up fabrication of more sophisticated functional nanostructures.
在过去的十年中，表面合成一直是一个研究热点。已经在表面上开发了各种化学反应来制备化合物和碳纳米结构，其中大多数都集中在碳-碳键形成上。尽管迄今为止已经取得了巨大的进展，但在表面合成中，有机化学中官能团的多样性还远远没有得到探索。在此，我们通过 Ag(111) 上羟甲基取代基的偶联反应研究了醚的表面辅助合成。通过使用两个具有不同对称性的羟甲基取代基功能化的分子前体，我们实现了醚链和环的形成。高分辨率扫描隧道显微镜结合密度泛函理论计算用于支持我们的发现，并为反应提供了机理见解。这项工作扩展了表面反应的工具包，用于自下而上制造更复杂的功能纳米结构。
