On-Surface Synthesis of Nonmetal Porphyrins.

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.

At the interface between organic radicals and TiO2(110) single crystals: electronic structure and paramagnetic character.

We find that in a paramagnetic pyrene derivative of the nitronyl nitroxide radical deposited on rutile TiO2(110) single crystals the molecules keep/lose their paramagnetic character depending on the local substrate hydroxylation. The first molecular layer may act as a "buffer" on which intact organic magnets are grown.