LAUSR

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.