Jump to main content
Jump to site search


On-surface transmetalation of metalloporphyrins

Author affiliations

Abstract

Increasing the complexity of 2D metal–organic networks has led to the fabrication of structures with interesting magnetic and catalytic properties. However, increasing complexity by providing different coordination environments for different metal types imposes limitations on their synthesis if the controlled placement of one metal type into one coordination environment is desired. Whereas metal insertion into free-base porphyrins at the vacuum/solid interface has been thoroughly studied, providing detailed insight into the mechanisms at play, the chemical interaction of a metal atom with a metallated porphyrin is rarely investigated. Herein, the breadth of metalation reactions is augmented towards the metal exchange of a metalloporphyrin through the deliberate addition of atomic metal centers. The cation of Fe(II)-tetraphenylporphyrins can be replaced by Co in a redox transmetalation-like reaction on a Au(111) surface. Likewise, Cu can be replaced by Co. The reverse reaction does not occur, i.e. Fe does not replace Co in the porphyrin. This non-reversible exchange is investigated in detail by X-ray absorption spectroscopy complemented by scanning tunneling microscopy. Density functional theory illuminates possible reaction pathways and leads to the conclusion that the transmetalation proceeds through the adsorption of initially metallic (neutral) Co onto the porphyrin and the expulsion of Fe towards the surface accompanied by Co insertion. Our findings have important implications for the fabrication of porphyrin layers on surfaces when subject to the additional deposition of metals. Mixed-metal porphyrin layers can be fabricated by design in a solvent-free process, but conversely care must be taken that the transmetalation does not proceed as an undesired side reaction.

Graphical abstract: On-surface transmetalation of metalloporphyrins

Back to tab navigation

Supplementary files

Publication details

The article was received on 12 Jun 2018, accepted on 25 Oct 2018 and first published on 26 Oct 2018


Article type: Paper
DOI: 10.1039/C8NR04786C
Citation: Nanoscale, 2018, Advance Article
  • Open access: Creative Commons BY license
  •   Request permissions

    On-surface transmetalation of metalloporphyrins

    D. Hötger, P. Abufager, C. Morchutt, P. Alexa, D. Grumelli, J. Dreiser, S. Stepanow, P. Gambardella, H. F. Busnengo, M. Etzkorn, R. Gutzler and K. Kern, Nanoscale, 2018, Advance Article , DOI: 10.1039/C8NR04786C

    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