Zinc-Porphine on Coinage Metal Surfaces: Adsorption Configuration and Ligand-Induced Central Atom Displacement

Aleksandr Baklanov, Johannes T. Küchle, David A. Duncan, Paul T.P. Ryan, Reinhard J. Maurer, Martin Schwarz, Eduardo Corral Rascon, Ignacio Piquero-Zulaica, Huynh Thien Ngo, Alexander Riss, Francesco Allegretti, Willi Auwärter

Research output: Contribution to journalArticlepeer-review

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.

Original languageEnglish
Pages (from-to)7501-7512
Number of pages12
JournalJournal of Physical Chemistry C
Volume127
Issue number15
DOIs
StatePublished - 20 Apr 2023

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