Molecular design driving tetraporphyrin self-assembly on graphite: A joint STM, electrochemical and computational study

M. El Garah, A. Santana Bonilla, A. Ciesielski, A. Gualandi, L. Mengozzi, A. Fiorani, M. Iurlo, M. Marcaccio, R. Gutierrez, S. Rapino, M. Calvaresi, F. Zerbetto, G. Cuniberti, P. G. Cozzi, F. Paolucci, P. Samorì

Research output: Contribution to journalArticle

Abstract

Tuning the intermolecular interactions among suitably designed molecules forming highly ordered self-assembled monolayers is a viable approach to control their organization at the supramolecular level. Such a tuning is particularly important when applied to sophisticated molecules combining functional units which possess specific electronic properties, such as electron/energy transfer, in order to develop multifunctional systems. Here we have synthesized two tetraferrocene-porphyrin derivatives that by design can selectively self-assemble at the graphite/liquid interface into either face-on or edge-on monolayer-thick architectures. The former supramolecular arrangement consists of two-dimensional planar networks based on hydrogen bonding among adjacent molecules whereas the latter relies on columnar assembly generated through intermolecular van der Waals interactions. Scanning Tunneling Microscopy (STM) at the solid-liquid interface has been corroborated by cyclic voltammetry measurements and assessed by theoretical calculations to gain multiscale insight into the arrangement of the molecule with respect to the basal plane of the surface. The STM analysis allowed the visualization of these assemblies with a sub-nanometer resolution, and cyclic voltammetry measurements provided direct evidence of the interactions of porphyrin and ferrocene with the graphite surface and offered also insight into the dynamics within the face-on and edge-on assemblies. The experimental findings were supported by theoretical calculations to shed light on the electronic and other physical properties of both assemblies. The capability to engineer the functional nanopatterns through self-assembly of porphyrins containing ferrocene units is a key step toward the bottom-up construction of multifunctional molecular nanostructures and nanodevices.

Original languageEnglish
Pages (from-to)13678-13686
Number of pages9
JournalNanoscale
Volume8
Issue number28
DOIs
Publication statusPublished - Jul 28 2016

Fingerprint

Graphite
Scanning tunneling microscopy
Self assembly
Porphyrins
Molecules
Cyclic voltammetry
Tuning
Liquids
Self assembled monolayers
Electronic properties
Energy transfer
Monolayers
Nanostructures
Hydrogen bonds
Visualization
Physical properties
Derivatives
Engineers
Electrons
ferrocene

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

El Garah, M., Santana Bonilla, A., Ciesielski, A., Gualandi, A., Mengozzi, L., Fiorani, A., ... Samorì, P. (2016). Molecular design driving tetraporphyrin self-assembly on graphite: A joint STM, electrochemical and computational study. Nanoscale, 8(28), 13678-13686. https://doi.org/10.1039/c6nr03424a

Molecular design driving tetraporphyrin self-assembly on graphite : A joint STM, electrochemical and computational study. / El Garah, M.; Santana Bonilla, A.; Ciesielski, A.; Gualandi, A.; Mengozzi, L.; Fiorani, A.; Iurlo, M.; Marcaccio, M.; Gutierrez, R.; Rapino, S.; Calvaresi, M.; Zerbetto, F.; Cuniberti, G.; Cozzi, P. G.; Paolucci, F.; Samorì, P.

In: Nanoscale, Vol. 8, No. 28, 28.07.2016, p. 13678-13686.

Research output: Contribution to journalArticle

El Garah, M, Santana Bonilla, A, Ciesielski, A, Gualandi, A, Mengozzi, L, Fiorani, A, Iurlo, M, Marcaccio, M, Gutierrez, R, Rapino, S, Calvaresi, M, Zerbetto, F, Cuniberti, G, Cozzi, PG, Paolucci, F & Samorì, P 2016, 'Molecular design driving tetraporphyrin self-assembly on graphite: A joint STM, electrochemical and computational study', Nanoscale, vol. 8, no. 28, pp. 13678-13686. https://doi.org/10.1039/c6nr03424a
El Garah M, Santana Bonilla A, Ciesielski A, Gualandi A, Mengozzi L, Fiorani A et al. Molecular design driving tetraporphyrin self-assembly on graphite: A joint STM, electrochemical and computational study. Nanoscale. 2016 Jul 28;8(28):13678-13686. https://doi.org/10.1039/c6nr03424a
El Garah, M. ; Santana Bonilla, A. ; Ciesielski, A. ; Gualandi, A. ; Mengozzi, L. ; Fiorani, A. ; Iurlo, M. ; Marcaccio, M. ; Gutierrez, R. ; Rapino, S. ; Calvaresi, M. ; Zerbetto, F. ; Cuniberti, G. ; Cozzi, P. G. ; Paolucci, F. ; Samorì, P. / Molecular design driving tetraporphyrin self-assembly on graphite : A joint STM, electrochemical and computational study. In: Nanoscale. 2016 ; Vol. 8, No. 28. pp. 13678-13686.
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