Odd−Even Effects at the S-Metal Interface and in the Aromatic Matrix of Biphenyl-Substituted Alkanethiol Self-Assembled Monolayers

Synchrotron-based high-resolution X-ray photoelectron spectroscopy was applied to characterize self-assembled monolayers (SAM) of biphenyl-substituted alkanethiols CH3(C6H4)2(CH2)nSH (BPn, n = 1−4) on Au and Ag substrates. Beyond previously identified odd−even changes in the packing density and the tilt angle of the biphenyl moieties, the high-resolution spectra reveal a number of additional odd−even effects upon variation of the number of methylene groups in the aliphatic part in the BPn molecule. Their occurrence and mutual correlation suggests that a BPn SAM represents a strongly correlated, highly ordered molecular assembly. In particular, periodical changes of a shake up feature in the C 1s region are observed, which are related to the differences in the arrangement of the aromatic matrix. The width and binding energy position of the S 2p signals also exhibit odd−even changes. The width changes are associated with the occupation of either equivalent or nonequivalent adsorption sites on the polycrystalline (111) Au and Ag substrates. The comparison of the width values with those for conventional alkanethiols implies that the substrate bonding of alkanethiols on gold cannot be described by a single adsorption site.