Abstract
Near-infrared surface-enhanced Raman spectroscopy and infrared reflection-absorption spectroscopy have been applied to investigate adsorption and ordering processes of resorcinarene cavitands at interfaces. Colloidal gold was applied in the case of NIR-Raman measurements, and planar gold substrates were used for reflection spectroscopy. Selected cavitands substituted on their upper rim with different functionalities were employed as probe molecules. An assignment of vibrational bands is presented. Interactions between probe molecules and substrates are present in all cases. From Raman measurements, it is difficult to deduce an orientation of the probe molecule adsorbed onto the gold particle, as the selection rules for SERS cannot be applied straightforwardly. Furthermore, an orientation depends on a proper assignment of vibrational bands. Infrared spectroscopy shows that the orientation of the resorcinarene molecules deposited on a planar gold or gold/monolayer interface is influenced by the underlying substrate. The directing effect, however, does not extend into the adjoining bulk of the sample layer.
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