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Direct quantitative identification of the "surface trans-effect"
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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. P., Duncan, David A. and Allegretti, Francesco (2016) Direct quantitative identification of the "surface trans-effect". Chemical Science, 7 (9). pp. 5647-5656. doi:10.1039/c6sc01677d ISSN 2041-6520.
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WRAP-direct-quantitiative-indentification-surface-Rochford-2016.pdf - Published Version - Requires a PDF viewer. Available under License Creative Commons Attribution. Download (705Kb) | Preview |
Official URL: https://doi.org/10.1039/c6sc01677d
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.
Item Type: | Journal Article | ||||||||||||||||||
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Subjects: | Q Science > QD Chemistry | ||||||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Physics |
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SWORD Depositor: | Library Publications Router | ||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Coordination compounds, Metals -- Surfaces, Absorption | ||||||||||||||||||
Journal or Publication Title: | Chemical Science | ||||||||||||||||||
Publisher: | Royal Society of Chemistry | ||||||||||||||||||
ISSN: | 2041-6520 | ||||||||||||||||||
Official Date: | 9 June 2016 | ||||||||||||||||||
Dates: |
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Volume: | 7 | ||||||||||||||||||
Number: | 9 | ||||||||||||||||||
Page Range: | pp. 5647-5656 | ||||||||||||||||||
DOI: | 10.1039/c6sc01677d | ||||||||||||||||||
Status: | Peer Reviewed | ||||||||||||||||||
Publication Status: | Published | ||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | ||||||||||||||||||
Date of first compliant deposit: | 2 October 2018 | ||||||||||||||||||
Date of first compliant Open Access: | 2 October 2018 | ||||||||||||||||||
RIOXX Funder/Project Grant: |
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