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)

Matthias Lischka; Georg S. Michelitsch; Natalia Martsinovich; Johanna Eichhorn; Atena Rastgoo-Lahrood; Thomas Strunskus; Rochus Breuer; Karsten Reuter; Michael Schmittel; Markus Lackinger

doi:10.1039/C8NR01987H

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)†

Matthias Lischka,^ab Georg S. Michelitsch,

^c Natalia Martsinovich,

^d Johanna Eichhorn,^ab Atena Rastgoo-Lahrood,^ab Thomas Strunskus,^e Rochus Breuer,^f Karsten Reuter,^c Michael Schmittel

^f and Markus Lackinger

*^abg

Author affiliations

* Corresponding authors

^a Department of Physics, Technische Universität München, James-Frank-Str. 1, 85748 Garching, Germany
E-mail: markus@lackinger.org

^b Center for NanoScience (CENS) & Nanosystems-Initiative-Munich, Schellingstr. 4, 80799 München, Germany

^c Chair for Theoretical Chemistry and Catalysis Research Center, Technische Universität München, Lichtenbergstraße 4, 85747 Garching, Germany

^d Department of Chemistry, University of Sheffield, Sheffield S3 7HF, UK

^e Institute of Materials Science – Multicomponent Materials, Christian-Albrecht-Universität zu Kiel, Kaiserstr. 2, 24143 Kiel, Germany

^f Center of Micro- and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein-Str. 2, 57068 Siegen, Germany

^g Deutsches Museum, Museumsinsel 1, 80538 Munich, Germany

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.

Nanoscale

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)†

Abstract

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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)

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