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

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...

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Main Authors: Aitchison, Hannah (Author) , Ortiz de la Morena, Rodrigo (Author) , Peifer, Raphael (Author) , Omar, Suhad (Author) , Lu, Hao (Author) , Francis, Stephen M. (Author) , Zharnikov, Michael (Author) , Grohmann, Andreas (Author) , Buck, Manfred (Author)
Format: Article (Journal)
Language:English
Published: July 24, 2018
In: Langmuir
Year: 2018, Volume: 34, Issue: 33, Pages: 9654-9664
ISSN:1520-5827
DOI:10.1021/acs.langmuir.8b01734
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.langmuir.8b01734
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Author Notes:Hannah Aitchison, Rodrigo Ortiz de la Morena, Raphael Peifer, Suhad Omar, Hao Lu, Stephen M. Francis, Michael Zharnikov, Andreas Grohmann, and Manfred Buck

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520 |a 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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