Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures

On-surface reactions based on Ullmann coupling are known to proceed on coinage-metal substrates (e.g. Au, Ag, Cu), with the chemistry of the surface strongly influencing the reaction progression. In addition, the topography of the surface may be expected to affect the local adsorption geometry of th...

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Main Authors: Judd, Chris J., Haddow, Sarah Louise, Champness, Neil R., Saywell, Alexander
Format: Article
Published: Nature Publishing Group 2017
Online Access:https://eprints.nottingham.ac.uk/47473/
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author Judd, Chris J.
Haddow, Sarah Louise
Champness, Neil R.
Saywell, Alexander
author_facet Judd, Chris J.
Haddow, Sarah Louise
Champness, Neil R.
Saywell, Alexander
author_sort Judd, Chris J.
building Nottingham Research Data Repository
collection Online Access
description On-surface reactions based on Ullmann coupling are known to proceed on coinage-metal substrates (e.g. Au, Ag, Cu), with the chemistry of the surface strongly influencing the reaction progression. In addition, the topography of the surface may be expected to affect the local adsorption geometry of the reactants as well as the intermediate and final structures. Here, we investigate the effect of two different surface facets of silver, Ag(111) and Ag(110) on the formation of organometallic and covalent structures for Ullmann-type coupling reactions. Deposition of 4,4”-diiodo-m-terphenyl molecules onto either Ag(111) or Ag(110) surfaces leads to the scission of C-I bonds followed by the formation of organometalic zigzag structures, consisting of molecules connected by coordination bonds to Ag adatoms. The covalently coupled product is formed by annealing each surface, leading to the removal of Ag atoms and the formation of covalently bonded zigzag poly(m-phenylene) structures. Comparisons of the adsorption model of molecules on each surface before and after annealing reveal that on Ag(111), structures rearrange by rotation and elongation of bonds in order to become commensurate with the surface, whereas for the Ag(110) surface, the similarity in adsorption geometry of the intermediate and final states means that no rotation is required.
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spelling nottingham-474732020-05-04T19:16:20Z https://eprints.nottingham.ac.uk/47473/ Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures Judd, Chris J. Haddow, Sarah Louise Champness, Neil R. Saywell, Alexander On-surface reactions based on Ullmann coupling are known to proceed on coinage-metal substrates (e.g. Au, Ag, Cu), with the chemistry of the surface strongly influencing the reaction progression. In addition, the topography of the surface may be expected to affect the local adsorption geometry of the reactants as well as the intermediate and final structures. Here, we investigate the effect of two different surface facets of silver, Ag(111) and Ag(110) on the formation of organometallic and covalent structures for Ullmann-type coupling reactions. Deposition of 4,4”-diiodo-m-terphenyl molecules onto either Ag(111) or Ag(110) surfaces leads to the scission of C-I bonds followed by the formation of organometalic zigzag structures, consisting of molecules connected by coordination bonds to Ag adatoms. The covalently coupled product is formed by annealing each surface, leading to the removal of Ag atoms and the formation of covalently bonded zigzag poly(m-phenylene) structures. Comparisons of the adsorption model of molecules on each surface before and after annealing reveal that on Ag(111), structures rearrange by rotation and elongation of bonds in order to become commensurate with the surface, whereas for the Ag(110) surface, the similarity in adsorption geometry of the intermediate and final states means that no rotation is required. Nature Publishing Group 2017-11-06 Article PeerReviewed Judd, Chris J., Haddow, Sarah Louise, Champness, Neil R. and Saywell, Alexander (2017) Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures. Scientific Reports, 7 (14541). pp. 1-7. ISSN 2045-2322 https://www.nature.com/articles/s41598-017-13315-1 doi:10.1038/s41598-017-13315-1 doi:10.1038/s41598-017-13315-1
spellingShingle Judd, Chris J.
Haddow, Sarah Louise
Champness, Neil R.
Saywell, Alexander
Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures
title Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures
title_full Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures
title_fullStr Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures
title_full_unstemmed Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures
title_short Ullmann coupling reactions on Ag(111) and Ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures Metal-Organic Structures
title_sort ullmann coupling reactions on ag(111) and ag(110); substrate influence on the formation of covalently coupled products and intermediate metal-organic structures metal-organic structures
url https://eprints.nottingham.ac.uk/47473/
https://eprints.nottingham.ac.uk/47473/
https://eprints.nottingham.ac.uk/47473/