Switching the electronic properties of Co-octaethylporphyrin molecules on oxygen-covered Ni films by NO adsorption

Using x-ray absorption spectroscopy, we demonstrate that the electronic properties of Co-octaethylporphyrin (CoOEP) molecules on oxygen-covered ultrathin Ni films can be reversibly manipulated by a chemical stimulus. This is achieved by adsorption of nitrogen monoxide (NO), leading to the formation of a NO-CoOEP nitrosyl complex, and subsequent thermal desorption of the NO from the Co ions. The integration of the absorption spectra of the Co L-2,L-3 edges reveals a partial oxidation of the Co ions after dosing with NO compared to the pristine sample, for which a valency of 2+ and a low-spin state of the Co ions can be deduced from the Co L-2,L-3 XAS line shape. By means of x-ray magnetic circular dichroism the magnetic moments of the Co ions were found to be coupled parallel to the magnetization of the Ni films across the intermediate layer of atomic oxygen, before and after NO uptake.