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

Dos Santos AC, De Campos Ferreira RC, Moreno-Lopez JC, Barreto L, Lepper M, Landers R, Steinrück HP, Marbach H, De Siervo A (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Chemistry of Materials American Chemical Society

Book Volume: 32

Pages Range: 2114-2122

Journal Issue: 5

DOI: 10.1021/acs.chemmater.9b05256

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-tetrakis(p-cyano)phenylporphyrin (2H-TCNPP) on Cu(111) using scanning tunneling microscopy. Upon co-deposition 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.

Authors with CRIS profile

Michael Lepper Lehrstuhl für Physikalische Chemie II Hans-Peter Steinrück Lehrstuhl für Physikalische Chemie II Hubertus Marbach Lehrstuhl für Physikalische Chemie II

Involved external institutions

Universidade Estadual de Campinas (UNICAMP) / University of Campinas BR Brazil (BR) Medizinische Universität Wien AT Austria (AT) Universidade Federal do ABC (UFABC) / Federal University of ABC BR Brazil (BR)

How to cite

APA:

Dos Santos, A.C., De Campos Ferreira, R.C., Moreno-Lopez, J.C., Barreto, L., Lepper, M., Landers, R.,... De Siervo, A. (2020). Cyano-Functionalized Porphyrins on Cu(111) from One-Dimensional Wires to Two-Dimensional Molecular Frameworks: On the Role of Co-Deposited Metal Atoms. Chemistry of Materials, 32(5), 2114-2122. https://doi.org/10.1021/acs.chemmater.9b05256

MLA:

Dos Santos, Alisson Ceccatto, et al. "Cyano-Functionalized Porphyrins on Cu(111) from One-Dimensional Wires to Two-Dimensional Molecular Frameworks: On the Role of Co-Deposited Metal Atoms." Chemistry of Materials 32.5 (2020): 2114-2122.

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