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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
Journal of the American Chemical Society, 03/2021, Volume: 143, Issue: 11Journal Article
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.
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