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Regensburg 2025 – scientific programme

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O: Fachverband Oberflächenphysik

O 17: Poster Focus Session Molecular Nanostructures on Surfaces: On-Surface Synthesis and Single-Molecule Manipulation

O 17.11: Poster

Monday, March 17, 2025, 18:00–20:00, P2

Metallocorroles: On-Surface Synthesis, Adsorption Geometry, and Electronic Structure — •Cong Guo, Jan Herritsch, Anastasiya Beliakouskaya, and J. Michael Gottfried — Philipps-Universität Marburg, Fachbereich Chemie, 35043 Marburg, Germany

Tetrapyrrolic macrocycles are widely recognized as fundamental building blocks for interfacial covalent architectures with remarkable stability and atomic precision. Corrole complexes are particularly notable due to their nature as trianionic ligands providing a contracted coordination environment. Herein, we report the on-surface formation and reaction of an octaalkyl-substituted magnesium corrole and an iron triphenylcorrole (FeTPC) on Ag(111). The free-base octaalkyl-corrole forms a well-ordered overlayer . Upon vapor deposition of Mg, the metal atoms incorporate into the corrole cavity, forming Mg-corrole complexes. However, XPS and STM studies show that excessive Mg deposition induces structural deformation and alters the electronic properties of the complex. FeTPC forms different long-range ordered adsorbate structures on Ag(111). During annealing, the degradation of FeTPC occurs, with cyclodehydrogenation leading to the planarization of the ligands, as indicated by XPS and STM. In addition, the ligation of nitric oxide at the Fe center, resulting in significant changes in the electronic properties of the complex, was investigated. These findings highlight the tunability of corrole complexes for tailored applications in catalysis and materials science.

Keywords: tetrapyrrolic macrocycle; corrole complexes; cyclodehydrogenation; electronic properties

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