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dc.contributor.authorAitchison, Hannah
dc.contributor.authorLu, Hao
dc.contributor.authorHogan, Simon William Leslie
dc.contributor.authorFruchtl, Herbert Anton
dc.contributor.authorCebula, Izabela
dc.contributor.authorZharnikov, Michael
dc.contributor.authorBuck, Manfred
dc.identifier.citationAitchison , H , Lu , H , Hogan , S W L , Fruchtl , H A , Cebula , I , Zharnikov , M & Buck , M 2016 , ' Self-assembled monolayers of oligophenylenecarboxylic acids on silver formed at the liquid-solid interface ' , Langmuir , vol. 32 , no. 37 , pp. 9397-9409 .
dc.identifier.otherPURE: 245294467
dc.identifier.otherPURE UUID: 75c972d2-68ed-4b61-bc12-986556adb06d
dc.identifier.otherScopus: 84988654474
dc.identifier.otherORCID: /0000-0003-1225-7607/work/56861194
dc.identifier.otherWOS: 000384038200003
dc.identifier.otherORCID: /0000-0001-6647-4266/work/60887473
dc.descriptionSupport by The Leverhulme Trust (RGP-2013-177) and EPSRC via a doctoral training grant (H.A.) is gratefully acknowledged.en
dc.description.abstractA series of para-oligophenylene mono- and dicarboxylic acids (R-(C6H4)nCOOH, n = 1-3, R = H,COOH) was studied. Adsorbed on Au(111)/mica modified by an underpotential deposited bilayer of Ag, the self-assembled monolayers (SAMs) were analysed by near edge X-ray absorption fine structure spectroscopy, X-ray photoelectron spectroscopy and scanning tunneling microscopy. In all cases SAMs are formed with molecules adopting an upright orientation and anchored to the substrate by a carboxylate. Except benzoic acid, all SAMs could be imaged at molecular resolution, which revealed highly crystalline layers with a dense molecular packing. The structures of the SAMs are described by a rectangular (5×√3) unit cell for the prevailing phase of the monocarboxylic acids and an oblique (√93×√133) unit cell for the dicarboxylic acids, thus, evidencing a pronounced influence of the second COOH moiety on the SAM structure. Density functional theory calculations suggest that hydrogen bonding between the SAM terminating COOH moieties accounts for the difference. Contrasting other classes of SAMs, the systems studied here are determined by intermolecular interactions whereas molecule-substrate interactions play a secondary role. Thus, eliminating problems arising from the mismatch between the molecular and substrate lattices, coordinatively bonded carboxylic acids on silver should provide considerable flexibility in the design of SAM structures.
dc.rightsCopyright © 2016 American Chemical Society. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at
dc.subjectCarboxylic acidsen
dc.subjectMetal-organic coordination bondingen
dc.subjectMolecular self-assemblyen
dc.subjectLiquid-solid interfaceen
dc.subjectUnderpotential depositionen
dc.subjectQD Chemistryen
dc.titleSelf-assembled monolayers of oligophenylenecarboxylic acids on silver formed at the liquid-solid interfaceen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.description.statusPeer revieweden

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