Cyano-Functionalized Porphyrins on Cu(111) from One-Dimensional Wires to Two-Dimensional Molecular Frameworks: On the Role of Co-Deposited Metal Atoms

Author(s)
Alisson Ceccatto dos Santos, Rodrigo Cezar de Campos Ferreira, Juan Carlos Moreno-Lopez, Lucas Barreto, Michael Lepper, Richard Landers, Hans-Peter Steinrück, Hubertus Marbach, Abner de Siervo
Abstract

Metal adatoms play a key role in surface diffusion, adsorption conformation, and self-assembly of porphyrin molecules on metal surfaces. Herein, we study the specific influence of coadsorption of Fe, Co, and Pd atoms on the behavior of 2H-tetiakis(p-cyano)phenylporphyrin (2H-TCNPP) on Cu(111) using scanning tunneling microscopy. Upon codeposition of Fe and Co, the molecules form one-dimensional (1D) linear chains after mild annealing on Cu(111) driven by the interaction of its cyano groups with metal adatoms. A similar behavior has been observed previously on Cu(111), mediated by Cu adatoms, where the functional CN groups were also found to lower the reaction rate of the so-called porphyrin self-metalation reaction with Cu atoms significantly, in comparison to the non-cyano-functionalized porphyrin. Upon co-deposition of Pd and mild annealing, we find a remarkably different behavior, that is, a massive reorganization from 1D molecular chains to a peculiar rectangular 2D (two-dimensional) network. The molecular appearance changes to a clover shape, which is attributed to a Pd-induced dehydrogenation and subsequent ring closure reaction of the phenyl and pyrrole groups.

Organisation(s)
Electronic Properties of Materials
External organisation(s)
Universidade Estadual de Campinas, Yachay Tech University, Universidade Federal do ABC, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU)
Journal
Chemistry of Materials
Volume
32
Pages
2114-2122
No. of pages
9
ISSN
0897-4756
DOI
https://doi.org/10.1021/acs.chemmater.9b05256
Publication date
03-2020
Peer reviewed
Yes
Austrian Fields of Science 2012
104017 Physical chemistry, 103018 Materials physics
Keywords
Portal url
https://ucris.univie.ac.at/portal/en/publications/cyanofunctionalized-porphyrins-on-cu111-from-onedimensional-wires-to-twodimensional-molecular-frameworks-on-the-role-of-codeposited-metal-atoms(3334fa31-0947-434f-834b-ea067b926ef9).html