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Instruments / Technical Area	Publication Details	Published	Actions
I09-Surface and Interface Structural Analysis	Zinc-porphine on coinage metal surfaces: adsorption configuration and ligand-induced central atom displacement Aleksandr Baklanov , Johannes T. Kuchle , David A. Duncan , Reinhard J. Maurer , Martin Schwarz , Eduardo Corral Rascon , Ignacio Piquero-Zulaica , Huynh Thien Ngo , Alexander Riss , Francesco Allegretti , Willi Auwärter , Paul T. P. Ryan The Journal Of Physical Chemistry C 35 DOI: 10.1021/acs.jpcc.3c00232 Diamond Proposal Number(s): [18874, 24276] Show Abstract ▼ Abstract: We present a comprehensive, quantitative multimethod characterization of the geometric and electronic interfacial structure of zinc-porphine (Zn-P) on coinage metal supports, namely, Ag(111) and Cu(111). Complementary techniques including X-ray standing waves, X-ray photoelectron spectroscopy, scanning tunneling microscopy, bond-resolved atomic force microscopy, and density functional theory calculations reveal the molecular conformations, signal a temperature-dependence of element-specific adsorption heights, rule out a decisive role of the d10 nature of the Zn center for the adsorption configuration, and uncover a considerably increased Zn-P adsorption height on Ag(111) compared to Cu(111). Furthermore, a pronounced out-of-plane displacement of the Zn center upon water ligation is demonstrated, a manifestation of the surface trans-effect. This study thus sheds light on effects of temperature, chemical nature of the metal center, its ligation, and the coinage metal support on interfacial structure and molecular deformation of an archetypical surface-anchored metal-tetrapyrrole.	Apr 2023
I09-Surface and Interface Structural Analysis	N-heterocyclic carbenes: molecular porters of surface mounted Ru-porphyrins Peter Knecht , Dennis Meier , Joachim Reichert , David A. Duncan , Martin Schwarz , Johannes Kuchle , Tien-Lin Lee , Peter Deimel , Peter Feulner , Francesco Allegretti , Willi Auwärter , Guillaume Médard , Ari P. Seitsonen , Johannes V. Barth , Anthoula Papageorgiou Angewandte Chemie International Edition DOI: 10.1002/anie.202211877 Diamond Proposal Number(s): [17634] Open Access Show Abstract ▼ Abstract: Ru-porphyrins act as convenient pedestals for the assembly of N-heterocyclic carbenes (NHCs) on solid surfaces. Upon deposition of a simple NHC ligand on a close packed Ru-porphyrin monolayer, an extraordinary phenomenon can be observed: Ru-porphyrin molecules are transferred from the silver surface to the next molecular layer. We have investigated the structural features and dynamics of this portering process and analyzed the associated binding strengths and work function changes. A rearrangement of the molecular layer is induced by the NHC uptake: the NHC selective binding to the Ru atoms causes the ejection of whole porphyrin molecules from the molecular layer on silver to the layer on top. This reorganization can be reversed by thermally induced desorption of the NHC ligand. We anticipate that the understanding of such mass transport processes will have crucial implications for the functionalization of surfaces with carbenes.	Oct 2022

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