Comparative Study of the Adsorption of Thiols and Selenols on Au(111) and Au(100).

The effect of the Au crystalline plane on the adsorption of different thiols and selenols is studied via reductive desorption (RD) and X-ray photoelectron spectroscopy (XPS) measurements. Self-assembled monolayers (SAMs) using aliphatic (ATs) and aromatic thiols (ArTs) on both Au(111) and Au(100) were prepared. The electrochemical stability of these SAMs on both surfaces is evaluated by comparing the position of the RD peaks. The longer the AT chain the more stable the SAM on Au(100) when compared to Au(111). By means of XPS measurements, we determine that the binding energy (BE) of the S 2p signal corresponding to the S atoms at the thiol/Au interface, commonly assigned at 162.0 eV, shifts 0.2 eV from Au(111) to Au(100) for SAMs prepared using thiols with the C* (C atom bonded to S) in sp3 hybridization, such as ATs. However, when the thiol presents the C* with an sp2 hybridization, such as in the case of ArTs, the BE remains at 162.0 eV regardless of the surface plane. Selenol-based SAMs were characterized comparatively on both Au(100) and Au(111). Our results show that selenol SAMs become even more electrochemically stable on Au(100) with respect to Au(111) than the analogue sulfur-based SAM. According to our results, we suggest that the electronic distribution around the Au-S/Se bond could be responsible for the different structural arrangements reported in the literature (gold adatoms, etc.), which should be dependent on the crystalline face (Au(hkl)-S) and the chemical nature of the environment of the adsorbates (sp3-C* vs sp2-C* and Au-SR vs Au-SeR).

A pH-Sensitive Supramolecular Switch Based on Mixed Carboxylic Acid Terminated Self-Assembled Monolayers on Au(111).

We show that homogeneously mixed self-assembled monolayers (SAMs) of mercaptoalkanoic acids of different chain lengths can be used to build up a pH-sensitive supramolecular switch. The acids with short and long alkyl chains interact via the strong hydrogen bond between carboxylic acid groups. The pH acts as a trigger by breaking or restoring the hydrogen bond interaction in basic or acidic solutions, respectively. The corresponding changes in the monolayer structure were determined by ellipsometry, surface-enhanced Raman spectroscopy, and contact angle measurements. Density functional theory (DFT) calculations were performed to elucidate the structures of interacting molecules compatible with the surface coverage obtained from electrochemical reductive desorption experiments. The simplicity of the preparation procedure assures a high reproducibility whereas the stability of the homogeneous mixed SAM guarantees the reversibility of the switching process.