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

Allen, Alexander; Abdur Rashid, Mohammad; Rahe, Philipp; Jarvis, Samuel P.; O'Shea, James N.; Dunn, Janette L.; Moriarty, Philip

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 etal. 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.

Citation

Allen, A., Abdur Rashid, M., Rahe, P., Jarvis, S. P., O'Shea, J. N., Dunn, J. L., & Moriarty, P. (2023). Self-assembly and tiling of a prochiral hydrogen-bonded network: bi-isonicotinic acid on coinage metal surfaces. Molecular Physics, 121(7-8), Article e2192824. https://doi.org/10.1080/00268976.2023.2192824

• Journal Article Type: Article
• Acceptance Date: Mar 11, 2023
• Online Publication Date: Mar 30, 2023
• Publication Date: 2023
• Deposit Date: Mar 20, 2023
• Publicly Available Date: Mar 31, 2024
• Journal: Molecular Physics
• Print ISSN: 0026-8976
• Electronic ISSN: 1362-3028
• Publisher: Informa UK Limited
• Peer Reviewed: Peer Reviewed
• Volume: 121
• Issue: 7-8
• Article Number: e2192824
• DOI: https://doi.org/10.1080/00268976.2023.2192824
• Keywords: Self-assembly; bi-isonicotinic acid; scanning tunnelling microscopy; atomic force microscopy; Monte Carlo simulation
• Public URL: https://nottingham-repository.worktribe.com/output/18760509
• Additional Information: Peer Review Statement: The publishing and review policy for this title is described in its Aims & Scope.; Aim & Scope: http://www.tandfonline.com/action/journalInformation?show=aimsScope&journalCode=tmph20; Received: 2022-09-30; Accepted: 2023-03-10; Published: 2023-03-30