Tunable Thiolate Coordination Networks on Metal Surfaces

Abstract Thiolate coordination networks (TCNs) were synthesized on metal surfaces using benzenehexathiol (BHT) and analyzed by cryogenic scanning tunneling microscopy (STM), X‐ray photoelectron spectroscopy (XPS) as well as density functional theory. Upon adsorption, the deprotonation of the thiol groups occurred on the metal surface with the formation of metal‐sulfur coordination bonds. Increasing the surface temperature triggered the complete dehydrogenation of BHT and promoted the formation of TCNs. On Ag(111), the TCN of [Ag₃(C₆S₆)]_n was achieved and showed good thermal stability. On Cu(111), two TCNs ([Cu₆(C₆S₆)]_n and [Cu₈(C₆S₆)]_n,) were identified. Interestingly, the construction of the two TCNs on Cu(111) can be precisely controlled by adjusting the temperature of the surface during deposition and thermal annealing. Our results reveal the significant influence of the metal surface on the formation of coordination networks.