Journal
LANGMUIR
Volume 34, Issue 33, Pages 9654-9664Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.langmuir.8b01734
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Funding
- EPSRC
- German Academic Exchange Service (DAAD)
- German Research Society (DFG)
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Monolayers of 4-(2,6-di(1H-pyrazol-1-yl)-pyridine-4-yObenzoic 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 angstrom(2). The DPP units adopt a trans trans conformation as inferred from the N is 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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