Adsorption and self-assembly of aromatic carboxylic acids on Au/electrolyte interfaces

Abstract

The adsorption and self-assembly of benzoic acid (BA), isophthalic acid (IA), and trimesic acid (TMA) on Au(111) single crystals and on Au(111-25 nm) quasi-single crystalline film electrodes have been investigated in 0.1 M HClO4 by combining in situ surface-enhanced infrared reflection absorption spectroscopy (SEIRAS) and scanning tunneling microscopy (STM) with cyclic voltammetry. All three acids are physisorbed on the electrode surface in a planar orientation at negative charge densities. Excursion to positive charge densities (or more positive potentials) causes an orientation change from planar to perpendicular. Chemisorbed structures are formed through the coordination of a deprotonated carboxyl group to the positively charged electrode surface. The three acid molecules assemble in different ordered patterns, which are controlled by pi-stacking (BA) or intermolecular hydrogen bonds between COOH groups (IA, TMA). A detailed analysis of the potential and time dependencies of the nu(C=O), nus(OCO), and nu(C-OH) vibration modes shows that the strength of lateral interactions increases upon chemisorption with an increasing number of COOH groups in the sequence of BA<IA<TMA. The vibration bands shift to higher wavenumbers due to dipole-dipole coupling, Stark tuning, and electron back donation from the electrode to COO-. In addition, an "indirect" electron donation to the COOH groups takes place via the conjugated molecular skeleton superimposed on the intermolecular hydrogen bonding.