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

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/H 2O 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. Finally, this apparent σ-donor nature of the observed STE on Ag(111) is shown to involve bondingmore » 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.« less

Authors:
 [1];  [2];  [2];  [3];  [4];  [5];  [5];  [6];  [1];  [7];  [8];  [1]
  1. Technische Univ. of Munich (Germany). Physics Dept.
  2. Univ. of Oklahoma, Norman, OK (United States). Center for Interfacial Reaction Engineering, School of Chemical, Biological and Materials Engineering
  3. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.; Univ. of Warwick, Coventry (United Kingdom). Dept. of Physics
  4. Univ. of Warwick, Coventry (United Kingdom). Dept. of Chemistry
  5. Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
  6. Univ. Paris Sciences & Lettres (PSL), Paris (France). ENS - Dept. of Chemistry
  7. Univ. of Warwick, Coventry (United Kingdom). Dept. of Physics
  8. Technische Univ. of Munich (Germany). Physics Dept.; Science and Technology Facilities Council (STFC), Harwell Campus, Oxford (United Kingdom). Diamond Light Source, Ltd.
Publication Date:
Research Org.:
Univ. of Oklahoma, Norman, OK (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1435768
Grant/Contract Number:  
SC0004600; 247299; EP/H021388/1
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 9; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Deimel, Peter S., Bababrik, Reda M., Wang, Bin, Blowey, Phil J., Rochford, Luke A., Thakur, Pardeep K., Lee, Tien-Lin, Bocquet, Marie-Laure, Barth, Johannes V., Woodruff, D. Phil, Duncan, David A., and Allegretti, Francesco. Direct quantitative identification of the “surface trans-effect”. United States: N. p., 2016. Web. doi:10.1039/c6sc01677d.
Deimel, Peter S., Bababrik, Reda M., Wang, Bin, Blowey, Phil J., Rochford, Luke A., Thakur, Pardeep K., Lee, Tien-Lin, Bocquet, Marie-Laure, Barth, Johannes V., Woodruff, D. Phil, Duncan, David A., & Allegretti, Francesco. Direct quantitative identification of the “surface trans-effect”. United States. doi:10.1039/c6sc01677d.
Deimel, Peter S., Bababrik, Reda M., Wang, Bin, Blowey, Phil J., Rochford, Luke A., Thakur, Pardeep K., Lee, Tien-Lin, Bocquet, Marie-Laure, Barth, Johannes V., Woodruff, D. Phil, Duncan, David A., and Allegretti, Francesco. Thu . "Direct quantitative identification of the “surface trans-effect”". United States. doi:10.1039/c6sc01677d. https://www.osti.gov/servlets/purl/1435768.
@article{osti_1435768,
title = {Direct quantitative identification of the “surface trans-effect”},
author = {Deimel, Peter S. and Bababrik, Reda M. and Wang, Bin and Blowey, Phil J. and Rochford, Luke A. and Thakur, Pardeep K. and Lee, Tien-Lin and Bocquet, Marie-Laure and Barth, Johannes V. and Woodruff, D. Phil and Duncan, David A. and Allegretti, Francesco},
abstractNote = {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. Finally, 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.},
doi = {10.1039/c6sc01677d},
journal = {Chemical Science},
number = 9,
volume = 7,
place = {United States},
year = {2016},
month = {6}
}

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