Formation of Hybrid Electronic States in FePc Chains Mediated by the Au(110) Surface

Iron–phthalocyanine (FePc) molecules deposited on the Au(110) surface self-organize in ordered chains driven by the reconstructed Au channels. The interaction process induces a rehybridization of the electronic states localized on the central metal atom, breaking the 4-fold symmetry of the molecular orbitals of the FePc molecules. The molecular adsorption is controlled by a symmetry-determined mixing between the electronic states of the Fe metal center and of the Au substrate, as deduced by photoemission and absorption spectroscopy exploiting light polarization. DFT calculations rationalize this mixing of the Fe and Au states on the basis of symmetry arguments. The calculated electronic structure reproduces the main experimental spectral features, which are associated to a distorted molecular structure displaying a trigonal bipyramidal geometry of the ligands around the metal center

Adsorption and Dissociation of <i>R</i>‑Methyl <i>p</i>‑Tolyl Sulfoxide on Au(111)

Sulfur-based molecules producing self-assembled monolayers on gold surfaces have long since become relevant functional molecular materials with many applications in biosensing, electronics, and nanotechnology. Among the various sulfur-containing molecules, the possibility to anchor a chiral sulfoxide to a metal surface has been scarcely investigated, despite this class of molecules being of great importance as ligands and catalysts. In this work, (R)-(+)-methyl p-tolyl sulfoxide was deposited on Au(111) and investigated by means of photoelectron spectroscopy and density functional theory calculations. The interaction with Au(111) leads to a partial dissociation of the adsorbate due to S–CH3 bond cleavage. The observed kinetics support the hypotheses that (R)-(+)-methyl p-tolyl sulfoxide adsorbs on Au(111) in two different adsorption arrangements endowed with different adsorption and reaction activation energies. The kinetic parameters related to the adsorption/desorption and reaction of the molecule on the Au(111) surface have been estimated