Adsorption Behavior of a Cyano-Functionalized Porphyrin on Cu(111) and Ag(111): From Molecular Wires to Ordered Supramolecular Two-Dimensional Aggregates

Journal article


Publication Details

Author(s): Lepper M, Schmitt T, Gurrath M, Raschmann M, Zhang L, Stark MW, Hölzel H, Jux N, Meyer B, Schneider MA, Steinrück HP, Marbach H
Journal: Journal of Physical Chemistry C
Publisher: AMER CHEMICAL SOC
Publication year: 2017
Volume: 121
Journal issue: 47
Pages range: 26361-26371
ISSN: 1932-7447
eISSN: 1932-7455


Abstract


We investigate the impact of peripheral cyano functionalization of the previously well-studied 2H-tetraphenylporphyrin (2HTPP) by scanning tunneling microscopy (STM) and density functional theory (DFT). The adsorption behavior of 2H-tetralds(p-cyano)-phenylporphyrin (2HTCNPP) is studied at room temperature and at 80 K on Cu(111) and Ag(111). Interestingly, the cyano-functionalized porphyrins tend to form isolated ID chains on Cu(111), in particular after mild annealing at 350 K. The individual 2HTCNPPs as well as the formed chains are oriented along the main crystallographic directions of the Cu(111) substrate due to a strongly attractive and site-specific interaction between the iminic nitrogens of the 2HTCNPP and Cu substrate atoms. The linking within the 1D molecular chains is realized by Cu adatoms as evidenced by comparison of STM and DFT. In contrast, on Ag(111) the molecules assemble into 2D supramolecular layers with long-range order and a square unit cell, stabilized by molecule-molecule interactions. The orientation of the molecules with respect to the unit cell lattice vectors leads to organizational chirality. By codeposition of cobalt, the porphyrin molecules are metalated at room temperature. We did not observe any evidence for metal-organic network formation on Ag(111), even after varying the deposition parameters or the order of metal and porphyrin deposition. Our study shows that cyano functionalization of porphyrins can give rise to novel and unique self-assembled structures like 1D molecular chains without any cross-connections via adatom linking.



FAU Authors / FAU Editors

Gurrath, Martin
Interdisziplinäres Zentrum für Molekulare Materialien
Lehrstuhl für Festkörperphysik
Hölzel, Helen
Schneider, M. Alexander Prof. Dr.
Interdisziplinäres Zentrum für Molekulare Materialien
Jux, Norbert Prof. Dr.
Interdisziplinäres Zentrum für Molekulare Materialien
Lepper, Michael
Lehrstuhl für Physikalische Chemie II
Marbach, Hubertus PD Dr.
Lehrstuhl für Physikalische Chemie II
Meyer, Bernd Prof. Dr.
Professur für Computational Chemistry
Raschmann, Marco
Lehrstuhl für Experimentalphysik (Alexander-von-Humboldt-Professur)
Schmitt, Tobias
Professur für Experimentalphysik
Stark, Michael Werner
Lehrstuhl für Physikalische Chemie II
Steinrück, Hans-Peter Prof. Dr.
Lehrstuhl für Physikalische Chemie II
Zhang, Liang Dr.
Lehrstuhl für Physikalische Chemie II


Additional Organisation
Exzellenz-Cluster Engineering of Advanced Materials


Research Fields

D Catalytic Materials
Exzellenz-Cluster Engineering of Advanced Materials
A3 Multiscale Modeling and Simulation
Exzellenz-Cluster Engineering of Advanced Materials


How to cite

APA:
Lepper, M., Schmitt, T., Gurrath, M., Raschmann, M., Zhang, L., Stark, M.W.,... Marbach, H. (2017). Adsorption Behavior of a Cyano-Functionalized Porphyrin on Cu(111) and Ag(111): From Molecular Wires to Ordered Supramolecular Two-Dimensional Aggregates. Journal of Physical Chemistry C, 121(47), 26361-26371. https://dx.doi.org/10.1021/acs.jpcc.7b08382

MLA:
Lepper, Michael, et al. "Adsorption Behavior of a Cyano-Functionalized Porphyrin on Cu(111) and Ag(111): From Molecular Wires to Ordered Supramolecular Two-Dimensional Aggregates." Journal of Physical Chemistry C 121.47 (2017): 26361-26371.

BibTeX: 

Last updated on 2019-06-08 at 09:05