Conformational Control of Chemical Reactivity for Surface‐Confined Ru‐Porphyrins

Peter Knecht (1) , Joachim Reichert (1) , Peter Deimel (1) , Peter Feulner (1) , Felix Haag (1) , Francesco Allegretti (1) , Manuela Garnica (1) , Martin Schwarz (1) , Willi Auwärter (1) , Paul Ryan (2, 3) , Tien‐lin Lee (2) , David Duncan (2) , Ari Paavo Seitsonen (4, 5, 6, 7) , Johannes Barth (1) , Anthoula Papageorgiou (1)

1 Physics Department E20
2 Diamond Light Source
3 Imperial College London
4 Département de Chimie, École Normale Supérieure
5 PSL - Université de recherche Paris-Sciences-et-Lettres
6 SU - Sorbonne Université
7 CNRS - Centre National de la Recherche Scientifique

We assess the crucial role of tetrapyrrole flexibility in the CO ligation to distinct Ru-porphyrins supported on an atomistically well-defined Ag(111) substrate. Our systematic real-space visualisation and manipulation experiments with scanning tunnelling microscopy directly probe the ligation, while bond-resolving atomic force microscopy and X-ray standing-wave measurements characterise the geometry, X-ray and ultraviolet photoelectron spectroscopy the electronic structure, and temperature-programmed desorption the binding strength. Density-functional-theory calculations provide additional insight into the functional interface. We unambiguously demonstrate that the substituents regulate the interfacial conformational adaptability, either promoting or obstructing the uptake of axial CO adducts.

Domains: Physics [physics]

Peter Knecht, Joachim Reichert, Peter Deimel, Peter Feulner, Felix Haag, et al.. Conformational Control of Chemical Reactivity for Surface‐Confined Ru‐Porphyrins. Angewandte Chemie, 2021, 133 (30), pp.16697-16703. ⟨10.1002/ange.202104075⟩. ⟨cea-04076225⟩