Ozonolysis-based route to the in situ formation of aldehyde-bearing self-assembled monolayer surfaces

While ozonolysis of a terminal carbon-carbon double bond to produce aldehydes is a well-established synthetic strategy for conventional solution chemistry, exposure of vinyl-terminated self-assembled monolayers to ozone has been reported to yield carboxylic acids. By using a cold solution of ozone in methanol and then adding a reducing agent to this solution, acid formation is minimized and near-quantitative aldehyde formation is achieved. The aldehyde-bearing surface is characterized by its physical and chemical properties and by ATR-FTIR spectroscopy showing a characteristic aldehyde C-H peak at 2715 cm(-1) and carbonyl peak at 1729 cm-1. The reactivity of the aldehyde-bearing surface is shown by its reaction with amines and amine derivatives to give surface-bound imines and by the reversible cycling between aldehyde and acetal. The acetal also provides a useful way to mask the aldehyde and store readily released aldehyde surface functionality for subsequent surface elaboration.