Cobalt atoms drive the anchoring of Co-TPP molecules to the oxygen-passivated Fe(0 0 1) surface

We present a multitechnique investigation of the structural and electronic properties of the prototypical system composed by ultra-thin films of magnetic molecules [Co-tetraphenyl-porphyrins (Co-TPP)] grown on a ferromagnetic substrate [oxygen passivated Fe(0 0 1), namely the Fe(0 0 1)-p(1 × 1)O surface]. Low Energy electron diffraction (LEED) and scanning tunneling microscopy (STM), coupled with first-principles calculations, reveal the formation of a commensurate superstructure at monolayer coverage, made by a square array of flat-lying TPP molecules. UV–photoemission and inverse photoemission spectroscopies (UPS and IPES) are used to investigate their electronic structure. Similar to our previous results on the Zn–TPP growth on Fe(0 0 1)–p(1 × 1)O, the passivation of the metallic surface is able to preserve the photoemission features characteristic of quasi-free molecules, opening the route towards an exploitation of single oxide layers as protective films in organic/inorganic junctions. X-ray photoemission (XPS) and near edge X-ray adsorption fine structure spectroscopies (NEXAFS), are used to reveal the details of the Co–TPP interaction with the substrate.