Zinc-Porphine on Coinage Metal Surfaces: Adsorption Configuration and Ligand-Induced Central Atom Displacement
Zinc-Porphine on Coinage Metal Surfaces: Adsorption Configuration and Ligand-Induced Central Atom Displacement
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DOI：
10.1021/acs.jpcc.3c00232
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发表时间：
2023-04-10
影响因子：
3.7
通讯作者：
Auwaerter，Willi
中科院分区：
文献类型：
--
作者：
Baklanov，Aleksandr;Kuechle，Johannes T.;Auwaerter，Willi
我们提出了一个全面的、定量的多方法表征锌-卟啉在铸币金属载体上的几何和电子界面结构，即银(111)和铜(111)。包括X射线驻波、X射线光电子能谱、扫描隧道显微镜、键分辨原子力显微镜和密度泛函理论计算在内的辅助技术揭示了分子构象，表明元素特定的吸附高度与温度有关，排除了锌中心的d10性质对吸附构型的决定性作用，并发现与铜(111)相比，锌-磷在Ag(111)上的吸附高度显著增加。此外，在水连接时，锌中心发生了明显的平面外移位，这是表面反转效应的表现。因此，这项研究揭示了温度、金属中心的化学性质、金属中心的配位以及铸币金属载体对典型的表面锚定金属-四吡咯的界面结构和分子形变的影响。
We present a comprehensive, quantitative multimethod characterization of the geometric and electronic interfacial structure of zinc-porphine (Zn-P) on coinage metal supports, namely, Ag(111) and Cu(111). Complementary techniques including X-ray standing waves, X-ray photoelectron spectroscopy, scanning tunneling microscopy, bond-resolved atomic force microscopy, and density functional theory calculations reveal the molecular conformations, signal a temperature-dependence of element-specific adsorption heights, rule out a decisive role of the d10nature of the Zn center for the adsorption configuration, and uncover a considerably increased Zn-P adsorption height on Ag(111) compared to Cu(111). Furthermore, a pronounced out-of-plane displacement of the Zn center upon water ligation is demonstrated, a manifestation of the surfacetrans-effect. This study thus sheds light on effects of temperature, chemical nature of the metal center, its ligation, and the coinage metal support on interfacial structure and molecular deformation of an archetypical surface-anchored metal-tetrapyrrole.