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Self-assembly of di(pyrazol-1-yl)pyridine-benzoic acid on underpotentially deposited Ag from solution

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Author(s)

Hannah Aitchison, Rodrigo Ortiz De La Morena, Raphael Peifer, Suhad Omar, Hao Lu, Stephen M. Francis, Michael Zharnikov, Andreas Grohmann, Manfred Buck

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Abstract

Monolayers of 4-(2,6-di(1H-pyrazol-1-yl)pyridine-4-yl)benzoic acid (DPP-BA) on Au substrates modified by an underpotential-deposited bilayer of Ag were studied by X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy, and scanning tunneling microscopy. Highly crystalline layers are formed with molecules coordinatively bonding to the surface through the carboxylate moiety in a bidentate configuration. The molecules assemble to rows characterized by densely packed upright-orientated DPP units occupying an area of 41 Å2. The DPP units adopt a trans-trans conformation as inferred from the N 1s XPS spectra taken at different photon energies. Their alignment alternates between adjacent rows, giving rise to a herringbone pattern. The pronouncedly different structure of the weakly commensurate self-assembled monolayer (SAM) of DPP-BA on Ag compared to the commensurate SAM of a DPP thiol on Au is a manifestation of the shift from substrate-directed assembly in the latter case to assembly dominated by intermolecular interactions in the former case.

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Details

Original languageEnglish
Pages (from-to)9654-9664
Number of pages11
JournalLangmuir
Volume34
Issue number33
Early online date24 Jul 2018
DOIs
Publication statusPublished - 21 Aug 2018

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