Resolving intramolecular-distortion changes induced by the partial fluorination of pentacene adsorbed on Cu(111)

Abstract

We experimentally quantify the molecular bending of a partially fluorinated pentacene (PEN) compound, namely 2,3,9,10-tetrafluoropentacene (F4PEN), adsorbed on Cu(111). By means of the x-ray standing wave (XSW) technique, we directly measure the adsorption distance of three inequivalent carbon sites, the fluorine atoms as well as the total and backbone carbon average adsorption distances. The precise positioning of different sites within the carbon core allows us to resolve two adsorption behaviors, namely a PEN-like strong coupling between the backbone and the substrate, and a repulsive interaction involving the fluorinated short molecular edges, which are $0.91\ifmmode\pm\else\textpm\fi{}0.09\phantom{\rule{4pt}{0ex}}\AA{}$ above the central benzene ring. This finding is further supported by additional electronic and in-plane-structure measurements, thus showing that the selective fluorination of a PEN molecule has only a local conformational effect and it is not sufficient to modify its interface properties. Yet, in the multilayer regime, the electronic and growth properties of the film differ completely from those of PEN and its perfluorinated derivative.