Final published version
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Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
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TY - JOUR
T1 - Self-assembly and tiling of a prochiral hydrogen-bonded network
T2 - bi-isonicotinic acid on coinage metal surfaces
AU - Allen, Alexander
AU - Abdur Rashid, Mohammad
AU - Rahe, Philipp
AU - Jarvis, Samuel P.
AU - O'Shea, James N.
AU - Dunn, Janette L.
AU - Moriarty, Philip
PY - 2023/7/31
Y1 - 2023/7/31
N2 - 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.
AB - 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.
KW - Physical and Theoretical Chemistry
KW - Condensed Matter Physics
KW - Molecular Biology
KW - Biophysics
U2 - 10.1080/00268976.2023.2192824
DO - 10.1080/00268976.2023.2192824
M3 - Journal article
VL - 121
JO - Molecular Physics
JF - Molecular Physics
SN - 0026-8976
IS - 7-8
M1 - e2192824
ER -