Writing with Molecules: Tip-Induced Local Chemisorption of N-Heterocyclic Olefins on Cu(111)

Landwehr, Felix; Das, Ankita; Tosoni, Sergio; Navarro, Juan J.; Das, Mowpriya; Glorius, Frank; Heyde, Markus; Roldan Cuenya, Beatriz

Forschungsartikel (Zeitschrift) | Peer reviewed

Zusammenfassung

N-Heterocyclic olefins (NHOs), possessing highly polarizable electron-rich double bonds, have recently received increased attention as promising ligands to modify the properties of various surfaces such as Cu, Au, and Si. This work demonstrates the precise “writing” of molecules on a Cu(111) surface by using the electric field of a scanning tunneling microscope (STM) tip. This selectively switches the molecules from a mobile, physisorbed state to a chemisorbed state with molecular, nanoscale spatial resolution under ultrahigh vacuum conditions. We utilize STM and high-resolution electron energy-loss spectroscopy supported by density-functional theory to investigate adsorption and orientation of the molecules on the Cu(111) surface. We find that IPr-NHO adopts two distinct adsorption states on Cu(111): a mobile, physisorbed state and a chemisorbed state. We can distinguish between the two states using X-ray photoelectron spectroscopy and show that the mobile species can be transformed into the immobile species via interaction with the STM tip with molecular precision. This enables “writing” of IPr-NHO on Cu(111) as the molecules can be chemisorbed in a predefined assembly in intentionally designed shapes, opening new possibilities for nanofabrication, molecular electronics, and tunable surface chemistry.

Details zur Publikation

Jahrgang / Bandnr. / Volume147
Ausgabe / Heftnr. / Issue31
Seitenbereich27676-27684
StatusVeröffentlicht
Veröffentlichungsjahr2025
DOI10.1021/jacs.5c06188
Link zum Volltexthttps://pubs.acs.org/doi/10.1021/jacs.5c06188
StichwörterAdsorption; Electric fields; Mathematical Methods; Molecules; Scanning tunneling microscopy

Autor*innen der Universität Münster

Das, Mowpriya
Professur für Organische Chemie (Prof. Glorius)
Das, Ankita
Professur für Organische Chemie (Prof. Glorius)
Glorius, Frank
Professur für Organische Chemie (Prof. Glorius)