Control of surface properties of self-assembled monolayers by tuning the degree of molecular asymmetry

We have studied self-assembled monolayers (SAMs) of asymmetric dialkyldisulfide derivatives of the form CH3–(CH2)11+m–S–S–(CH2)11–OH with m = −4, −3, 0, +2 and +4 on gold. Sub-nanoscale changes in the length of the CH3-terminated alkylchain have been used to selectively protrude one particular end group in the resulting film. The alteration of the chain length in only two methylene units already results in changes of surface properties, which have been detected with local (chemical force microscopy) and macroscopic (contact angle) techniques. In particular, advancing contact angles can be adjusted between 40° and 80°. The adhesion between a hydrophobic tip and these SAMs in water is determined by the chemical nature of the protruding end group. Chemical force microscopy, X-ray photoelectron spectroscopy and infrared reflection absorption spectroscopy have shown that these SAMs are composed of mixed, well-packed CH3– and OH–alkylthiolate branches. The surface composition ratio is close to 1:1 for all investigated SAMs.