Adsorption geometry, conformation, and electronic structure of 2H-octaethylporphyrin on Ag(111) and Fe metalation in ultra high vacuum

Due to the growing interest in the ferromagnetic properties of Fe-octaethylporphyrins (Fe-OEP) for applications in spintronics, methods to produce stable Fe-porphyrins with no Cl atoms are highly demanded. Here, we demonstrate the formation of Fe-OEP layers on Ag(111) single crystal by the ultra high vacuum in situ metalation of the free-base 2H-2,3,7,8,12,13,17,18-octaethylporphyrin (2H-OEP) molecules. The metalation proceeds exactly as in the case of 2H-5,10,15,20-tetraphenylporphyrin (2H-TPP) on the same substrate. An extensive surface characterization by means of X-ray photoemission spectroscopy, valence band photoemission, and NEXAFS with synchrotron radiation light provides information on molecular conformation and electronic structure in the monolayer and multilayer cases. We demonstrate that the presence of the ethyl groups affects the tilt of the adsorbed molecules, the conformation of the macrocycle, and the polarization screening in multilayers, but has only a minor effect in the metalation process with respect to 2H-TPP.This work is partially supported by the Italian Ministero dell’Istruzione, dell’Universitá e della Ricerca (FIRB Nanosolar RBAP11C58Y_003) and by the MIUR through the FIRB Futuro in Ricerca “SUPRACARBON” (contract No. RBFR10DAK6).Peer reviewe