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

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      Judd_et_al_Sci_Rep_2017_Data.zip (197.7Mb)
      Publication date
      2017-11-09
      Creators
      Judd, Chris J.
      Saywell, Alex
      Metadata
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      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.
      External URI
      • https://rdmc.nottingham.ac.uk/handle/internal/329
      DOI
      • http://doi.org/10.17639/nott.325
      Related publication DOI
      • 10.1038/s41598-017-13315-1
      Subjects
      • Surface chemistry
      • Silver -- Surfaces
      • Scanning probe microscopy
      • Catalysis
      • Chemical bonds -- Structure
      • on-surface synthesis, Ullmann coupling, scanning probe microscopy, cataylsis
      • Physical sciences::Chemistry::Physical chemistry
      • Physical sciences::Physics::Chemical physics, Solid-state physics
      • Q Science::QD Chemistry::QD450 Physical and theoretical chemistry
      Divisions
      • University of Nottingham, UK Campus::Faculty of Science::School of Physics and Astronomy
      • University of Nottingham, UK Campus::Faculty of Science::School of Chemistry
      Deposit date
      2017-11-09
      Data type
      Scanning tunnelling microscopy images (STM)
      Contributors
      • Haddow, Sarah L.
      • Champness, Neil R.
      Funders
      • Engineering & Physical Sciences Research Council
      • People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme
      • Royal Society Wolfson Merit Award
      Grant number
      • 623992-TOPCHEM
      • EP/K01773X/1
      Data collection method
      Scanning Tunelling Microscopy (STM): Omicron VT STM/AFM system
      Resource languages
      • en
      Publisher
      The University of Nottingham

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