Thioetherification of Br-Mercaptobiphenyl Molecules on Au(111).

Thioether polymers are fundamental for a variety of applications. Their synthesis is, however, more challenging than that of other metal-catalyzed reactions due to the reported detachment of the S atom during thermal activation. In this study, it has been demonstrated unambiguously that thermal annealing results in the thioetherification of the 4-bromo-4-mercaptobiphenyl molecule (Br-MBP) adsorbed on the surface of Au(111). Through complementary techniques, such as scanning tunneling microscopy, spectroscopy, and first-principle calculations, we have identified four reaction steps, involving sulfhydryl or bromine molecular functional groups and leading to the formation of intermolecular C-S bonds. To form the thioether polymer and to overcome the competitive formation of C-C bonds, two reaction steps, the dehalogenation, and dissociation of the S-Au bond, must occur simultaneously. We detail the electronic properties of the phenyl-sulfur bond and the polymer as a function of the ligand length. This result suggests a wider perspective of this chemical synthesis.