Lischka, M., Michelitsch, G.S., Martsinovich, N. orcid.org/0000-0001-9226-8175 et al. (7 more authors) (2018) Remote functionalization in surface-assisted dehalogenation by conformational mechanics: organometallic self-assembly of 3,3′,5,5′-tetrabromo-2,2′,4,4′,6,6′-hexafluorobiphenyl on Ag(111). Nanoscale. ISSN 2040-3364
Abstract
Even though the surface-assisted dehalogenative coupling constitutes the most abundant protocol in on-surface synthesis, its full potential will only become visible if selectivity issues with polybrominated precursors are comprehensively understood, opening new venues for both organometallic self-assembly and on-surface polymerization. Using the 3,3′,5,5′-tetrabromo-2,2′,4,4′,6,6′-hexafluorobiphenyl (Br4F6BP) at Ag(111), we demonstrate a remote site-selective functionalization at room temperature and a marked temperature difference in double- vs. quadruple activation, both phenomena caused by conformational mechanical effects of the precursor-surface ensemble. The submolecularly resolved structural characterization was achieved by Scanning Tunneling Microscopy, the chemical state was quantitatively assessed by X-ray Photoelectron Spectroscopy, and the analysis of the experimental signatures was supported through first-principles Density-Functional Theory calculations. The non-planarity of the various structures at the surface was specifically probed by additional Near Edge X-ray Absorption Fine Structure experiments. Upon progressive heating, Br4F6BP on Ag(111) shows the following unprecedented phenomena: (1) formation of regular organometallic 1D chains via remote site-selective 3,5′-didebromination; (2) a marked temperature difference in double- vs. quadruple activation; (3) an organometallic self-assembly based on reversibility of C–Ag–C linkages with a thus far unknown polymorphism affording both hexagonal and rectangular 2D networks; (4) extraordinary thermal stability of the organometallic networks. Controlled covalent coupling at the previously Br-functionalized sites was not achieved for the Br4F6BP precursor, in contrast to the comparatively studied non-fluorinated analogue.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018 Royal Society of Chemistry. This is an author produced version of a paper subsequently published in Royal Society of Chemistry. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 22 Jun 2018 10:15 |
Last Modified: | 06 Jun 2019 00:43 |
Published Version: | https://doi.org/10.1039/C8NR01987H |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Refereed: | Yes |
Identification Number: | 10.1039/C8NR01987H |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:132411 |