Thiolate versus selenolate: structure, stability, and charge transfer properties
Selenolate is considered as an alternative to thiolate to serve as a headgroup mediating the formation of self-assembled monolayers (SAMs) on coinage metal substrates. There are, however, ongoing vivid discussions regarding the advantages and disadvantages of these anchor groups, regarding, in parti...
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| Hauptverfasser: | , , , , , , , , , , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
April 10, 2015
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| In: |
ACS nano
Year: 2015, Jahrgang: 9, Heft: 4, Pages: 4508-4526 |
| ISSN: | 1936-086X |
| DOI: | 10.1021/acsnano.5b01109 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acsnano.5b01109 Verlag, lizenzpflichtig, Volltext: https://pubs.acs.org/doi/10.1021/acsnano.5b01109 
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| Verfasserangaben: | Jakub Ossowski, Tobias Wächter, Laura Silies, Martin Kind, Agnieszka Noworolska, Florian Blobner, Dominika Gnatek, Jakub Rysz, Michael Bolte, Peter Feulner, Andreas Terfort, Piotr Cyganik, and Michael Zharnikov |
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| 245 | 1 | 0 | |a Thiolate versus selenolate |b structure, stability, and charge transfer properties |c Jakub Ossowski, Tobias Wächter, Laura Silies, Martin Kind, Agnieszka Noworolska, Florian Blobner, Dominika Gnatek, Jakub Rysz, Michael Bolte, Peter Feulner, Andreas Terfort, Piotr Cyganik, and Michael Zharnikov |
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| 520 | |a Selenolate is considered as an alternative to thiolate to serve as a headgroup mediating the formation of self-assembled monolayers (SAMs) on coinage metal substrates. There are, however, ongoing vivid discussions regarding the advantages and disadvantages of these anchor groups, regarding, in particular, the energetics of the headgroup-substrate interface and their efficiency in terms of charge transport/transfer. Here we introduce a well-defined model system of 6-cyanonaphthalene-2-thiolate and -selenolate SAMs on Au(111) to resolve these controversies. The exact structural arrangements in both types of SAMs are somewhat different, suggesting a better SAM-building ability in the case of selenolates. At the same time, both types of SAMs have similar packing densities and molecular orientations. This permitted reliable competitive exchange and ion-beam-induced desorption experiments which provided unequivocal evidence for a stronger bonding of selenolates to the substrate as compared to the thiolates. Regardless of this difference, the dynamic charge transfer properties of the thiolate- and selenolate-based adsorbates were found to be nearly identical, as determined by the core-hole-clock approach, which is explained by a redistribution of electron density along the molecular framework, compensating the difference in the substrate-headgroup bond strength. | ||
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