Self-assembled monolayers of 4-mercaptopyridine on Au(111): A potential-induced phase transition in sulfuric acid solutions

In situ scanning tunneling microscopy images of self-assembled monolayers (SAMs) of 4-mercaptopyridine (4-MPy) on Au(111) recorded in neat 0.1 M H₂SO₄ solutions provided evidence for a potential-induced phase transition over the range 0.40-0.15 V versus saturated calomel electrode. Analysis of the data was consistent with the presence of a (5 × √3) and (10 × √3) superstructure (phase A) at the positive end, that is, 0.40 V, for which the local coverage, θ_loc, is about 0.2 (two 4-MPy molecules per unit cell), which compresses at the negative end, that is, 0.15 V, to yield a much denser superstructure (phase B, θ_loc ca. 0.5). This behavior is unlike that reported for the 4-MPy-Au(111) SAM prepared by identical means, in 0.1 M HClO₄ (or in sulfate solutions of a much higher pH) for which only the (5 × √3) superstructure was observed over the same potential range. The compression associated with the phase A to phase B transition is attributed to the formation of a hydrogen-bonded network of bisulfate coordinated in turn to the 4-MPy layer via the acidic hydrogens of the pyridinium moieties. Such conditions promote better packing of adsorbed 4-MPy species, which are aided by intermolecular π-π ring interactions, resulting in higher local coverages.