Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms
Competitive Metal Coordination of Hexaaminotriphenylene on Cu(111) by Intrinsic Copper Versus Extrinsic Nickel Adatoms
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DOI：
10.1002/chem.201803908
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发表时间：
2019-02-06
影响因子：
4.3
通讯作者：
Lackinger, Markus
中科院分区：
文献类型：
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作者：
Lischka, Matthias;Dong, Renhao;Lackinger, Markus
在超高真空条件下，通过高分辨率扫描隧道显微镜（STM）和X射线光电子能谱（XPS）互补研究了Cu（111）上2,3,6,7,10,11-六氨基苯并菲（HATP）的自组装和表面化学之间的相互作用。为了阐明竞争性金属配位，对原始 Cu(111) 和镍覆盖的 Cu(111) 进行了对比实验。 HATP 在室温下沉积到原始 Cu(111) 上后，立即通过 STM 观察到自组装聚集体，XPS 结果表明氨基仍质子化。 XP 光谱中 N 1s 和 C 1s 核心水平的化学位移表明，退火至 200 摄氏度激活了所有氨基的渐进式单去质子化。这使得能够形成具有内在铜吸附原子的拓扑多样的-d共轭配位网络。这些网络的基本基序是金属有机三聚体，其中三个 HATP 分子由 Cu-3 簇配位，随附的密度泛函理论 (DFT) 模拟证实了这一点。更多活性镍原子的额外沉积导致化学和结构变化，并在室温下发生去质子化和双（二亚氨基）-Ni键合网络的形成。尽管观察到了熔融六边形金属配位孔，但扩展的蜂窝网络仍然难以捉摸，正如这些金属有机键的可逆性有限所初步解释的那样。
The interplay between the self-assembly and surface chemistry of 2,3,6,7,10,11-hexaaminotriphenylene (HATP) on Cu(111) was complementarily studied by high-resolution scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) under ultra-high vacuum conditions. To shed light on the competitive metal coordination, comparative experiments were carried out on pristine and nickel-covered Cu(111). Directly after room-temperature deposition of HATP onto pristine Cu(111), self-assembled aggregates were observed by STM, and XPS results indicated still protonated amino groups. Annealing up to 200 degrees C activated the progressive single deprotonation of all amino groups as indicated by chemical shifts of both the N 1s and C 1s core levels in the XP spectra. This enabled the formation of topologically diverse -d conjugated coordination networks with intrinsic copper adatoms. The basic motif of these networks was a metal-organic trimer, in which three HATP molecules were coordinated by Cu-3 clusters, as corroborated by the accompanying density functional theory (DFT) simulations. Additional deposition of more reactive nickel atoms resulted in both chemical and structural changes with deprotonation and formation of bis(diimino)-Ni bonded networks already at room temperature. Even though fused hexagonal metal-coordinated pores were observed, extended honeycomb networks remained elusive, as tentatively explained by the restricted reversibility of these metal-organic bonds.