Tongji-Aarhus Joint Research Center for Nanostructures and Functional Nanomaterials, College of Materials Science and Engineering, Tongji University , Caoan Road 4800, Shanghai 201804, People's Republic of China.
ACS Nano. 2016 Jul 26;10(7):7023-30. doi: 10.1021/acsnano.6b03048. Epub 2016 Jun 24.
On-surface C-C coupling reactions of molecular precursors with alkynyl functional groups demonstrate great potential for the controllable fabrication of low-dimensional carbon nanostructures/nanomaterials, such as carbyne, graphyne, and graphdiyne, which demand the incorporation of highly active sp-hybridized carbons. Recently, through a dehydrogenative homocoupling reaction of alkynes, the possibility was presented to fabricate surface nanostructures involving acetylenic linkages, while problems lie in the fact that different byproducts are inevitably formed when triggering the reactions at elevated temperatures. In this work, by delicately designing the molecular precursors with terminal alkynyl bromide, we introduce the dehalogenative homocoupling reactions on the surface. As a result, we successfully achieve the formation of dimer structures, one-dimensional molecular wires and two-dimensional molecular networks with acetylenic scaffoldings on an inert Au(111) surface, where the unexpected C-Au-C organometallic intermediates are also observed. This study further supplements the database of on-surface dehalogenative C-C coupling reactions, and more importantly, it provides us an alternative efficient way for incorporating the acetylenic scaffolding into low-dimensional surface nanostructures.
表面分子前驱体与炔基官能团的 C-C 偶联反应，为可控合成低维碳纳米结构/纳米材料（如炔烃、炔基和炔基二炔）提供了巨大的潜力，这需要引入高活性的 sp 杂化碳。最近，通过炔烃的脱氢偶联反应，提出了在表面形成涉及炔键的纳米结构的可能性，然而，在高温下引发反应时，不可避免地会形成不同的副产物。在这项工作中，通过精心设计具有末端炔基溴的分子前驱体，我们在表面上引入了脱卤基偶联反应。结果，我们成功地在惰性 Au(111)表面上形成了二聚体结构、一维分子线和二维分子网络，其中还观察到了意想不到的 C-Au-C 有机金属中间体。这项研究进一步补充了表面脱卤 C-C 偶联反应的数据库，更重要的是，它为我们提供了一种将炔基支架纳入低维表面纳米结构的有效替代方法。
