NUK - logo
E-resources
Full text
Peer reviewed
  • On-Surface Synthesis of Non...
    Baklanov, Aleksandr; Garnica, Manuela; Robert, Anton; Bocquet, Marie-Laure; Seufert, Knud; Küchle, Johannes T; Ryan, Paul T. P; Haag, Felix; Kakavandi, Reza; Allegretti, Francesco; Auwärter, Willi

    Journal of the American Chemical Society, 01/2020, Volume: 142, Issue: 4
    Journal Article

    We report the on-surface synthesis of a nonmetal porphyrin, namely, silicon tetra­phenyl­porphyrin (Si-TPP), by the deposition of atomic silicon onto a free-base TPP layer on a Ag(100) surface under ultrahigh vacuum (UHV) conditions. Scanning tunneling microscopy provides insights into the self-assembly of the TPP molecules before and after Si insertion. Silicon coordinates with all four nitrogen atoms of the TPP macrocycle and interacts with a silver atom of the substrate as confirmed by scanning tunneling spectroscopy, X-ray photoelectron spectroscopy, and complementary density functional theory calculations. The Si-TPP complex presents a saddle-shaped conformation that is stable under STM manipulation. Our study shows how protocols established for the on-surface metalation of tetrapyrroles can be adopted to achieve nonmetal porphyrins. Complementary experiments yielding Si-TPP and Ge-TPP on Ag(111) highlight the applicability to different main group elements and supports. The success of our nonmetal porphyrin synthesis procedure is further corroborated by a temperature-programmed desorption experiment, revealing the desorption of Ge-TPP. This extension of interfacial complex formation beyond metal elements opens promising prospects for new tetrapyrrole architectures with distinct properties and functionalities.