与金（111）配位的中位-四（十二烷基）卟啉自组装单层膜。

Self-organized monolayer of meso-tetradodecylporphyrin coordinated to Au(111).

作者信息

Katsonis Nathalie, Vicario Javier, Kudernac Tibor, Visser Johan, Pollard Michael M, Feringa Ben L

机构信息

Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.

出版信息

J Am Chem Soc. 2006 Dec 6;128(48):15537-41. doi: 10.1021/ja065823o.

DOI:10.1021/ja065823o

PMID:17132021

Abstract

The structure of molecular monolayers formed at the interface between atomically flat surfaces and a solution of free-base meso-tetradodecylporphyrins (H2Ps) was examined by scanning tunneling microscopy (STM) at the liquid/solid interface. On the surface of graphite (HOPG), H2Ps form a well-ordered monolayer characterized by an oblique unit cell. On Au(111), H2Ps form a self-organized monolayer comprised of two distinct domain types. In both types of domains, the density of the porphyrin cores is increased in comparison to the arrangement observed on HOPG. Also, high-resolution STM images reveal that, in contrast to what is observed on HOPG, physisorption on Au(111) induces a distortion of the porphyrin macrocycle out of planarity. By using X-ray photoelectron spectroscopy, we demonstrate that this is likely to be due to the coordination of the lone pairs of the iminic (-C=N-) nitrogen atoms of the porphyrin macrocycle to Au(111).

摘要

通过扫描隧道显微镜（STM）在液/固界面研究了原子级平整表面与游离碱中位-四十二烷基卟啉（H2P）溶液界面处形成的分子单层结构。在石墨（HOPG）表面，H2P形成具有倾斜晶胞特征的有序单层。在Au(111)上，H2P形成由两种不同畴类型组成的自组装单层。在这两种畴类型中，与在HOPG上观察到的排列相比，卟啉核的密度增加。此外，高分辨率STM图像显示，与在HOPG上观察到的情况相反，在Au(111)上的物理吸附导致卟啉大环平面外扭曲。通过使用X射线光电子能谱，我们证明这可能是由于卟啉大环亚胺基（-C=N-）氮原子的孤对电子与Au(111)配位所致。