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首页> 外文期刊>Chemistry: A European journal >2H-Tetrakis(3,5-di-tert-butyl)phenylporphyrin on a Cu(110) Surface: Room-Temperature Self-Metalation and Surface-Reconstruction-Facilitated Self-Assembly
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2H-Tetrakis(3,5-di-tert-butyl)phenylporphyrin on a Cu(110) Surface: Room-Temperature Self-Metalation and Surface-Reconstruction-Facilitated Self-Assembly

机译：Cu（110）表面上的2H-四（3,5-二叔丁基）苯基卟啉：室温自金属化和表面重构促进的自组装

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摘要

The adsorption behavior of 2H-tetrakis(3,5-di-tert-butyl)phenylporphyrin (2HTTBPP) on Cu(110) and Cu(110)-(2x1)O surfaces have been investigated by using variable-temperature scanning tunneling microscopy (STM) under ultrahigh vacuum conditions. On the bare Cu(110) surface, individual 2HTTBPP molecules are observed. These molecules are immobilized on the surface with a particular orientation with respect to the crystallographic directions of the Cu(110) surface and do not form supramolecular aggregates up to full monolayer coverage. In contrast, a chiral supramolecular structure is formed on the Cu(110)-(2x1)O surface, which is stabilized by van der Waals interactions between the tert-butyl groups of neighboring molecules. These findings are explained by weakened molecule-substrate interactions on the Cu(110)-(2x1)O surface relative to the bare Cu(110) surface. By comparison with the corresponding results of Cu-tetrakis(3,5-di-tert-butyl)phenylporphyrin (CuTTBPP) on Cu(110) and Cu(110)-(2x1)O surfaces, we find that the 2HTTBPP molecules can self-metalate on both surfaces with copper atoms from the substrate at room temperature (RT). The possible origins of the self-metalation reaction at RT are discussed. Finally, peculiar irreversible temperature-dependent switching of the intramolecular conformations of the investigated molecules on the Cu(110) surface was observed and interpreted.
机译：已通过使用变温扫描隧道显微镜技术研究了2H-四（3,5-二叔丁基）苯基卟啉（2HTTBPP）在Cu（110）和Cu（110）-（2x1）O表面上的吸附行为（ STM）在超高真空条件下。在裸露的Cu（110）表面上，观察到单个2HTTBPP分子。这些分子以相对于Cu（110）表面的晶体学方向的特定方向固定在表面上，并且不会形成超分子聚集体，直至完全被单层覆盖。相反，在Cu（110）-（2x1）O表面上形成了手性超分子结构，该结构通过相邻分子的叔丁基之间的范德华相互作用而稳定。这些发现可以通过相对于裸露的Cu（110）表面在Cu（110）-（2x1）O表面上减弱的分子-底物相互作用来解释。通过与Cu（110）和Cu（110）-（2x1）O表面上的Cu-四（3,5-二叔丁基）苯基卟啉（CuTTBPP）的相应结果进行比较，我们发现2HTTBPP分子可以自我-在室温（RT）下用来自基板的铜原子在两个表面上金属化。讨论了在室温下自金属化反应的可能起源。最后，观察和解释了Cu（110）表面上所研究分子的分子内构象的独特的不可逆的温度依赖性转换。

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