Knecht Peter, Zhang Bodong, Reichert Joachim, Duncan David A, Schwarz Martin, Haag Felix, Ryan Paul T P, Lee Tien-Lin, Deimel Peter S, Feulner Peter, Allegretti Francesco, Auwärter Willi, Médard Guillaume, Seitsonen Ari Paavo, Barth Johannes V, Papageorgiou Anthoula C
Physics Department E20, Technical University of Munich, James Franck Straße 1, 85748 Garching, Germany.
Diamond Light Source, Harwell Science and Innovation Campus, Didcot OX11 0QX, U.K.
J Am Chem Soc. 2021 Mar 24;143(11):4433-4439. doi: 10.1021/jacs.1c01229. Epub 2021 Mar 11.
The controlled arrangement of N-heterocyclic carbenes (NHCs) on solid surfaces is a current challenge of surface functionalization. We introduce a strategy of using Ru porphyrins in order to control both the orientation and lateral arrangement of NHCs on a planar surface. The coupling of the NHC to the Ru porphyrin is a facile process which takes place on the interface: we apply NHCs as functional, robust pillars on well-defined, preassembled Ru porphyrin monolayers on silver and characterize these interfaces with atomic precision via a battery of experimental techniques and theoretical considerations. The NHCs assemble at room temperature modularly and reversibly on the Ru porphyrin arrays. We demonstrate a selective and complete functionalization of the Ru centers. With its binding, the NHC modifies the interaction of the Ru porphyrin with the Ag surface, displacing the Ru atom by 1 Å away from the surface. This arrangement of NHCs allows us to address individual ligands by controlled manipulation with the tip of a scanning tunneling microscope, creating patterned structures on the nanometer scale.
在固体表面对氮杂环卡宾（NHCs）进行可控排列是当前表面功能化面临的一项挑战。我们引入了一种使用钌卟啉的策略，以控制NHCs在平面表面上的取向和横向排列。NHC与钌卟啉的偶联是一个在界面上发生的简便过程：我们将NHC用作功能强大的支柱，置于银表面上定义明确的预组装钌卟啉单分子层上，并通过一系列实验技术和理论考量以原子精度表征这些界面。NHC在室温下以模块化且可逆的方式组装在钌卟啉阵列上。我们展示了钌中心的选择性和完全功能化。通过其结合，NHC改变了钌卟啉与银表面的相互作用，使钌原子从表面位移1 Å。这种NHC的排列方式使我们能够通过扫描隧道显微镜尖端的可控操作来处理单个配体，从而在纳米尺度上创建图案化结构。
