Neutral organic radical formation by chemisorption on metal surfaces
Organic radical monolayers (r-MLs) bonded to metal surfaces are potential materials for the development of molecular (spin)electronics. Typically, stable radicals bearing surface anchoring groups are used for generating r-MLs. Following a recent theoretical proposal based on a model system, we repor...
| Autores: | , , , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2020 |
| País: | España |
| Institución: | Universidad de Cantabria (UC) |
| Repositorio: | UCrea Repositorio Abierto de la Universidad de Cantabria |
| Idioma: | inglés |
| OAI Identifier: | oai:repositorio.unican.es:10902/34976 |
| Acceso en línea: | https://hdl.handle.net/10902/34976 |
| Access Level: | acceso abierto |
| Palabra clave: | Self-assembled monolayers Chemisorption X-ray photoelectron spectroscopy Angle-resolved photoelectron spectroscopy Stable radicals Density functional theory |
| Sumario: | Organic radical monolayers (r-MLs) bonded to metal surfaces are potential materials for the development of molecular (spin)electronics. Typically, stable radicals bearing surface anchoring groups are used for generating r-MLs. Following a recent theoretical proposal based on a model system, we report the first experimental realization of a metal surface induced r-ML where a rationally chosen closed-shell precursor 3,5-dichloro-[bis-(2,4,6- trichlorophenyl)methylen]cyclohexa-2,5-diene-1-one (1) transforms into a stable neutral openshell species (1•) via chemisorption on Ag(111) surface. X-ray photoelectron spectroscopy reveals that the >C=O group of 1 reacts with the surface forming a C-O-Ag linkage which induces an electronic rearrangement that transforms 1 to 1•. Importantly, Au is inert towards 1, while Cu surface leads to dehalogenation reactions. The radical nature of the monolayer was further confirmed by angle-resolved photoelectron spectroscopy and electronic structure calculations which provide evidence for the emergence of the singly occupied molecular orbital (SOMO) of 1•. |
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