Self-assembly and conformation of tetrapyridyl-porphyrin molecules on Ag(111)

• Published in: The Journal of chemical physics Vol. 124; no. 19; p. 194708
• Main Authors: Auwärter, W, Weber-Bargioni, A, Riemann, A, Schiffrin, A, Gröning, O, Fasel, R, Barth, J V
• Format: Journal Article
• Language: English
• Published: United States 21.05.2006
• Subjects: Microscopy, Scanning Tunneling - methods; Molecular Conformation; Porphyrins - chemistry; Silver - chemistry; Surface Properties
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.2194541

We present a low-temperature scanning tunneling microscopy (STM) study on the supramolecular ordering of tetrapyridyl-porphyrin (TPyP) molecules on Ag(111). Vapor deposition in a wide substrate temperature range reveals that TPyP molecules easily diffuse and self-assemble into large, highly ordered chiral domains. We identify two mirror-symmetric unit cells, each containing two differently oriented molecules. From an analysis of the respective arrangement it is concluded that lateral intermolecular interactions control the packing of the layer, while its orientation is induced by the coupling to the substrate. This finding is corroborated by molecular mechanics calculations. High-resolution STM images recorded at 15 K allow a direct identification of intramolecular features. This makes it possible to determine the molecular conformation of TPyP on Ag(111). The pyridyl groups are alternately rotated out of the porphyrin plane by an angle of 60 degrees.