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.
References:
On-Surface Synthesis of Nonmetal Porphyrins
Aleksandr Baklanov, Manuela Garnica, Anton Robert, Marie-Laure Bocquet, Knud Seufert, Johannes T. Küchle, Paul T. P. Ryan, Felix Haag, Reza Kakavandi, Francesco Allegretti, and Willi Auwar̈ter
J. Am. Chem. Soc. 2020, 142, 4, 1871-1881
DOI: 10.1021/jacs.9b10711