Structures of monolayers formed from different HS-(CH2)2-X thiols on gold, silver and copper:: comparitive studies by surface-enhanced Raman scattering

Molecules of 2-aminoethanethiol (cysteamine, CYS), 2-mercaptoethanol (MET), 3-mercaptopropionic acid (MPA), sodium 2-mercaptoethanesulphonate (MES) and 1-propanethiol (PTH) were spontaneously chemisorbed on electrochemically activated silver, copper and gold surfaces. The structure of monolayers formed was studied with surface-enhanced Raman scattering (SERS). In CYS and MPA monolayers the relative surface concentration of gauche conformers was higher than in MET, PTH and MES monolayers. This is probably due to double bonding to the metal surface by a fraction of adsorbed MPA and CYS molecules (via the sulphur moiety and the terminal carboxylic or amino group). In CYS, MET, MPA and PTH monolayers, the surface concentration of trans conformers is significantly higher on Ag than on Au or Cu. The structures of MES monolayers on Ag, Au and Cu are similar, with very high surface concentrations of trans conformers. Statistically, the wavenumbers of nu(C-S) bands of both gauche and trans conformers are the highest on Au, slightly lower on Ag and the lowest for Cu. However the positions of nu(C-S) bands are also sensitive to the other parameters (e.g. C - C - S - metal torsion angle, the overall ordering of the monolayer). Therefore, the wavenumbers of nu(C-S) bands are not good indicators of differences in the interaction between chemisorbed thiols and the metal substrates. Desorption measurements suggest that part of the adsorbed molecules is bonded significantly weaker than the rest. Thiolate monolayers on Cu decomposed relatively easily, forming a layer of copper sulphide. The strength of adsorbed MPA acid is similar on all substrates. Copyright (C) 2003 John Wiley Sons, Ltd.