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Self-assembly and tiling of a prochiral hydrogen-bonded network: bi-isonicotinic acid on coinage metal surfaces

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Published
  • Alexander Allen
  • Mohammad Abdur Rashid
  • Philipp Rahe
  • Samuel P. Jarvis
  • James N. O'Shea
  • Janette L. Dunn
  • Philip Moriarty
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Article numbere2192824
<mark>Journal publication date</mark>31/07/2023
<mark>Journal</mark>Molecular Physics
Issue number7-8
Volume121
Number of pages11
Publication StatusPublished
Early online date30/03/23
<mark>Original language</mark>English

Abstract

Submolecular resolution scanning tunnelling microscopy and qPlus atomic force microscopy reveal that, close to thermal equilibrium, bi-isonicotinic acid (4,4'-COOH-2,2'-bpy) assembles into extended molecular rows on both Au(111) and Ag(100) surfaces, driven primarily by the formation of OH··· N hydrogen bonds. Both the intermolecular separation and inter-row spacing for Au(111) and Ag(100) are identical within experimental uncertainty, highlighting that the assembly of bi-isonicotinic acid networks on both metal surfaces is predominantly driven by intermolecular hydrogen-bonding and that the potential energy variation due to the substrate has relatively little influence. Nonetheless, the surface plays a key role in molecular organisation: symmetry-breaking induces prochiral behaviour, which drives the molecular enantiomers to form a racemic mixture of rows of different handedness. We adapt a tiling model previously introduced to model the formation of 2D networks of tetracarboxylic derivatives [Blunt et al. Science322, 1077 (2008)] to the bi-isonicotinic acid system, providing key insights into the growth kinetics and attaining good agreement with the molecular morphologies observed in experiment.