title: Adsorption of fumaramide [2]rotaxane and its components on a solid substrate: a coverage-dependent study.
abstract: The coverage-dependent adsorption on Au(111) of a fumaramide [2]rotaxane and its components, a benzylic amide macrocycle and a fumaramide thread, is studied using high-resolution electron energy loss spectroscopy (HREELS). Up to monolayer coverage, the relative intensity of out-of-plane to in-plane phenyl ring vibrational modes indicates that the macrocycle adopts an orientation with the phenyl rings largely parallel to the surface. The formation of a chemisorption bond is evidenced by the presence of a Au-O stretching vibration. In contrast, the thread shows no evidence of chemisorption or a preferential orientation. The introduction of the thread into the macrocycle partly disrupts the film order so that the resulting chemisorbed rotaxane shows intermediate behavior with a preferential orientation up to 0.5 ML coverage. A decrease in film order and the absence of a preferred molecular orientation is observed for all three molecules at multilayer coverages. The spectral differences are addressed by molecular dynamics simulations in terms of the mobility of the phenyls of the three molecules on Au(111).
authors.affiliation: Laboratoire Interdisciplinaire de Spectroscopie Electronique, Facultés Universitaires Notre-Dame de la Paix, 61 Rue de Bruxelles, B-5000 Namur, Belgium.
authors.forename: Caroline M
authors.initials: CM
authors.lastname: Whelan
authors.forename: Francesco
authors.initials: F
authors.lastname: Gatti
authors.forename: David A
authors.initials: DA
authors.lastname: Leigh
authors.forename: Stefania
authors.initials: S
authors.lastname: Rapino
authors.forename: Francesco
authors.initials: F
authors.lastname: Zerbetto
authors.forename: Petra
authors.initials: P
authors.lastname: Rudolf