Jump to main content
Jump to site search

Issue 9, 2016
Previous Article Next Article

Direct quantitative identification of the “surface trans-effect”

Author affiliations

Abstract

The strong parallels between coordination chemistry and adsorption on metal surfaces, with molecules and ligands forming local bonds to individual atoms within a metal surface, have been established over many years of study. The recently proposed “surface trans-effect” (STE) appears to be a further manifestation of this analogous behaviour, but so far the true nature of the modified molecule–metal surface bonding has been unclear. The STE could play an important role in determining the reactivities of surface-supported metal–organic complexes, influencing the design of systems for future applications. However, the current understanding of this effect is incomplete and lacks reliable structural parameters with which to benchmark theoretical calculations. Using X-ray standing waves, we demonstrate that ligation of ammonia and water to iron phthalocyanine (FePc) on Ag(111) increases the adsorption height of the central Fe atom; dispersion corrected density functional theory calculations accurately model this structural effect. The calculated charge redistribution in the FePc/H2O electronic structure induced by adsorption shows an accumulation of charge along the σ-bonding direction between the surface, the Fe atom and the water molecule, similar to the redistribution caused by ammonia. This apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bonding to the delocalised metal surface electrons rather than local bonding to one or more surface atoms, thus indicating that this is a true surface trans-effect.

Graphical abstract: Direct quantitative identification of the “surface trans-effect”

Back to tab navigation

Supplementary files

Publication details

The article was received on 15 Apr 2016, accepted on 08 Jun 2016 and first published on 09 Jun 2016


Article type: Edge Article
DOI: 10.1039/C6SC01677D
Citation: Chem. Sci., 2016,7, 5647-5656
  • Open access: Creative Commons BY license
  •   Request permissions

    Direct quantitative identification of the “surface trans-effect”

    P. S. Deimel, R. M. Bababrik, B. Wang, P. J. Blowey, L. A. Rochford, P. K. Thakur, T. Lee, M. Bocquet, J. V. Barth, D. P. Woodruff, D. A. Duncan and F. Allegretti, Chem. Sci., 2016, 7, 5647
    DOI: 10.1039/C6SC01677D

    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