“…The attachment of trifluoroacetic anhydride (TFAA) to self-assembled monolayers presenting alcohol termini was selected as the model system for the present study. This reaction is known to proceed quickly both in solution , and in the vapor phase, and it is not thought to be complicated by uncontrollable side processes. , In the bulk phase, the trifluoroacetylation of alcohols with TFAA occurs via a straightforward esterification mechanism in which a tertiary amine base acts as a nucleophilic catalyst. , The conversion of an alcohol terminus to the corresponding trifluoroester group is desirable, as the functional group yields prominent, readily quantifiable peaks in infrared (IR) or X-ray photoelectron spectroscopy (XPS) spectra. ,,, This type of fluorine labeling has been used with great success on polymeric films, − in the study of the composition of mixed monolayers containing alcohol functionalities, and for investigations of the properties of hydroxyl-terminated SAMs including reaction kinetics. , However, the kinetics of the reaction have not previously been established. In terms of reactivity, interfaces often demonstrate unusual behavior that is not observed in the analogous bulk phase reaction.…”