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Structural information on the Au-S Interface of thiolate-protected gold clusters: A raman spectroscopy study


Varnholt, Birte; Oulevey, Patric; Luber, Sandra; Kumara, Chanaka; Dass, Amala; Buergi, Thomas (2014). Structural information on the Au-S Interface of thiolate-protected gold clusters: A raman spectroscopy study. Journal of Physical Chemistry C, 118(18):9604-9611.

Abstract

The Raman spectra of a series of monolayer-protected gold clusters were investigated with special emphasis on the Au-S modes below 400 cm(-1). These clusters contain monomeric (SR-Au-SR) and dimeric (SR-Au-SR-Au-SR) gold-thiolate staples in their surface. In particular, the Raman spectra of Au-25(2-PET)(18)](0/-), Au-38(2-PET)(24), Au-40(2-PET)(24), and Au-144(2-PET)(60) (2-PET = 2-phenylethylthiol) were measured in order to study the influence of the cluster size and therefore the composition with respect to the monomeric and dimeric staples. Additionally, spectra of Au-25(2-PET)(18-2x) (S-/rac-BINAS)(x) (BINAS = 1,1'-binaphthy1-2,2'-dithiol), Au-25(CamS)(18) (CamS = 1R,4S-camphorthiol), and Au(n)BINAS(m) were measured to identify the influence of the thiolate ligand on the Au-S vibrations. The vibrational spectrum of Au-38(SCH3)(24) was calculated which allows the assignment of bands to vibrational modes of the different staple motifs. The spectra are sensitive to the size of the cluster and the nature of the ligand. Au-S-C bending around 200 cm(-1) shifts to slightly higher wavenumbers for the dimeric as compared to the monomeric staples. Radial Au-S modes (250-325 cm(-1)) seem to be sensitive toward the staple composition and the bulkiness of the ligand, having higher intensities for long staples and shifting to higher wavenumbers for sterically more demanding ligands. The introduction of only one BINAS dithiol has a dramatic influence on the Au-S vibrations because the molecule bridges two staples which changes their vibrational properties completely.

Abstract

The Raman spectra of a series of monolayer-protected gold clusters were investigated with special emphasis on the Au-S modes below 400 cm(-1). These clusters contain monomeric (SR-Au-SR) and dimeric (SR-Au-SR-Au-SR) gold-thiolate staples in their surface. In particular, the Raman spectra of Au-25(2-PET)(18)](0/-), Au-38(2-PET)(24), Au-40(2-PET)(24), and Au-144(2-PET)(60) (2-PET = 2-phenylethylthiol) were measured in order to study the influence of the cluster size and therefore the composition with respect to the monomeric and dimeric staples. Additionally, spectra of Au-25(2-PET)(18-2x) (S-/rac-BINAS)(x) (BINAS = 1,1'-binaphthy1-2,2'-dithiol), Au-25(CamS)(18) (CamS = 1R,4S-camphorthiol), and Au(n)BINAS(m) were measured to identify the influence of the thiolate ligand on the Au-S vibrations. The vibrational spectrum of Au-38(SCH3)(24) was calculated which allows the assignment of bands to vibrational modes of the different staple motifs. The spectra are sensitive to the size of the cluster and the nature of the ligand. Au-S-C bending around 200 cm(-1) shifts to slightly higher wavenumbers for the dimeric as compared to the monomeric staples. Radial Au-S modes (250-325 cm(-1)) seem to be sensitive toward the staple composition and the bulkiness of the ligand, having higher intensities for long staples and shifting to higher wavenumbers for sterically more demanding ligands. The introduction of only one BINAS dithiol has a dramatic influence on the Au-S vibrations because the molecule bridges two staples which changes their vibrational properties completely.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Electronic, Optical and Magnetic Materials
Physical Sciences > General Energy
Physical Sciences > Physical and Theoretical Chemistry
Physical Sciences > Surfaces, Coatings and Films
Language:English
Date:2014
Deposited On:21 Oct 2014 12:26
Last Modified:30 Jul 2020 14:32
Publisher:American Chemical Society
ISSN:1932-7447
OA Status:Green
Publisher DOI:https://doi.org/10.1021/jp502453q

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