Berlin 2018 – wissenschaftliches Programm

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O: Fachverband Oberflächenphysik

O 78: Poster: Surface Dynamics - Reactions, Elementary Processes and Phase Transitions

O 78.11: Poster

Mittwoch, 14. März 2018, 18:15–20:30, Poster A

On the kinetics of the self-metalation reaction of 2H-tetraphenylporphyrin derivatives on Cu(111) with different peripheral CN functionalization — •Manuel Meusel, Michael Lepper, Julia Köbl, Hans-Peter Steinrück, and Hubertus Marbach — Lehrstuhl für Physikalische Chemie II, Universität Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany.

In this contribution, we present a detailed scanning tunneling microscopy (STM) study concerning the kinetics of the self-metalation reaction of 2H-tetraphenylporpporphyrins (2HTPP) on Cu(111) with and without peripheral cyano functionalization. The corresponding self-metalation reaction, in which the free base porphyrins metalate with Cu atoms from the substrate, has been studied intensively for 2HTPP on Cu(111) in the past [1-3]. Surprisingly, we observed a strong decrease of the self-metalation rate directly correlating to the degree of functionalization with peripheral cyano groups, opposed to the expected trend for a metalation in solution. Statistical analysis of isothermal STM time series allows for the estimation of corresponding changes in the activation energy of the self-metalation for the different porphyrin species. The origin of this phenomenon will be discussed in respect to different binding motifs and the intramolecular conformation of the porphyrins. This work was funded through DFG FOR 1878 (funCOS) under grant MA 4246/2 -1. [1] K. Diller et al., J. Chem. Phys., 136 (2012) 014705 [2]S. Dietze et al., Ang. Chem. Int. Ed. 51 (2012) 10898 [3] H. Marbach, Acc. Chem. Res., 48 (2015) 2649