Temperature-controlled metal/ligand stoichiometric ratio in Ag-TCNE coordination networks

The deposition of tetracyanoethylene (TCNE) on Ag(111), both at Room Temperature (RT, 300 K) and low temperatures (150 K), leads to the formation of coordination networks involving silver adatoms, as revealed by Variable-Temperature Scanning Tunneling Microscopy. Our results indicate that TCNE molecules etch away material from the step edges and possibly also from the terraces, which facilitates the formation of the observed coordination networks. Moreover, such process is temperature dependent, which allows for different stoichiometric ratios between Ag and TCNE just by adjusting the deposition temperature. X-ray Photoelectron Spectroscopy and Density Functional Theory calculations reveal that charge-transfer from the surface to the molecule and the concomitant geometrical distortions at both sides of the organic/inorganic interface might facilitate the extraction of silver atoms from the step-edges and, thus, its incorporation into the observed TCNE coordination networks.