Structure and Molecule–Substrate Interaction in a Co-octaethyl Porphyrin Monolayer on the Ag(110) Surface

We present a combined experimental and theoretical study of the ultrathin film of Co-octaethylporphyrin (Co-OEP) molecules deposited on the Ag(110) surface. The morphological and electronic properties of this heterogeneous metallorganic interface were studied by means of scanning tunneling microscopy (STM), near-edge X-ray adsorption fine structure (NEXAFS) spectroscopy, ultraviolet photoemission spectroscopy (UPS), and density functional theory calculations (DFT). The long-range self-ordered single layer of Co-OEP was obtained by thermal desorption of the molecular multilayer. The single-layer molecules were arranged in a noncommensurate rectangular lattice aligned with the substrate high-symmetry directions. The combination of experimental techniques and numerical simulations indicated that in this configuration each molecular macrocycle is tilted with respect to the metal surface of about 15°. The strong molecular interaction with the substrate leads to the electron transfer from the metal substrate to the molecule. The direct interaction with the substrate involves mostly the Co metal center, which modifies the valence state with respect to the free Co-OEP molecules due to the hybridization between Co states and Ag bands.