Jump to main content
Jump to site search

Issue 9, 2015
Previous Article Next Article

Surface-confined 2D polymerization of a brominated copper-tetraphenylporphyrin on Au(111)

Author affiliations

Abstract

A coupling-limited approach for the Ullmann reaction-like on-surface synthesis of a two-dimensional covalent organic network starting from a halogenated metallo-porphyrin is demonstrated. Copper-octabromo-tetraphenylporphyrin molecules can diffuse and self-assemble when adsorbed on the inert Au(111) surface. Splitting-off of bromine atoms bonded at the macrocyclic core of the porphyrin starts at room temperature after the deposition and is monitored by X-ray photoelectron spectroscopy for different annealing steps. Direct coupling between the reactive carbon sites of the molecules is, however, hindered by the molecular shape. This leads initially to an ordered non-covalently interconnected supramolecular structure. Further heating to 300 °C and an additional hydrogen dissociation step is required to link the molecular macrocycles via a phenyl group and form large ordered polymeric networks. This approach leads to a close-packed covalently bonded network of overall good quality. The structures are characterized using scanning tunneling microscopy. Different kinds of lattice defects and, furthermore, the impact of polymerization on the HOMO–LUMO gap are discussed. Density functional theory calculations corroborate the interpretations and give further insight into the adsorption of the debrominated molecule on the surface and the geometry and coupling reaction of the polymeric structure.

Graphical abstract: Surface-confined 2D polymerization of a brominated copper-tetraphenylporphyrin on Au(111)

Back to tab navigation

Publication details

The article was received on 29 Oct 2014, accepted on 02 Feb 2015 and first published on 03 Feb 2015


Article type: Paper
DOI: 10.1039/C4NR06371F
Author version
available:
Download author version (PDF)
Citation: Nanoscale, 2015,7, 4234-4241
  • Open access: Creative Commons BY license
  •   Request permissions

    Surface-confined 2D polymerization of a brominated copper-tetraphenylporphyrin on Au(111)

    L. Smykalla, P. Shukrynau, M. Korb, H. Lang and M. Hietschold, Nanoscale, 2015, 7, 4234
    DOI: 10.1039/C4NR06371F

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements