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On-surface synthesis of nonmetal porphyrins

DOI: 10.1021/jacs.9b10711 DOI Help

Authors: Aleksandr Baklanov (Technical University of Munich) , Manuela Garnica (Technical University Munich) , Anton Robert (PSL University, Sorbonne Université, CNRS) , Marie-laure Bocquet (PSL University, Sorbonne Université, CNRS) , Knud Seufert (Technical University of Munich) , Johannes T. Kuchle (Technical University of Munich) , Paul T. P. Ryan (Diamond Light Source; Imperial College London) , Felix Haag (Technical University Munich) , Reza Kakavandi (Technical University of Munich) , Francesco Allegretti (Technical University of Munich) , Willi Auwärter (Technical University of Munich)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Journal Of The American Chemical Society

State: Published (Approved)
Published: January 2020

Abstract: 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.

Subject Areas: Chemistry

Facility: SLS beamline X03DA (PEARL)