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.

中文翻译：

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金属表面上的可调节硫醇盐配位网络

使用苯六硫醇（BHT）在金属表面合成了硫氰酸盐配位网络（TCN），并通过低温扫描隧道显微镜（STM），X射线光电子能谱（XPS）以及密度泛函理论进行了分析。吸附后，巯基的去质子化在金属表面发生，形成金属-硫配位键。表面温度的升高触发了BHT的完全脱氢并促进了TCN的形成。在Ag（111）上，获得了[Ag ₃（C ₆ S ₆）] _n的TCN，并显示出良好的热稳定性。在Cu（111）上，两个TCN（[Cu ₆（C ₆ S ₆）] _n和[Cu ₈（C ₆ S ₆）] _n，）被鉴定。有趣的是，可以通过在沉积和热退火过程中调节表面温度来精确控制Cu（111）上两个TCN的结构。我们的结果揭示了金属表面对配位网络形成的重大影响。