Far-infrared spectra of well-defined thiolate-protected gold clusters

Dolamic, Igor; Varnholt, Birte; Bürgi, Thomas

doi:10.1039/c3cp53845a

Cited by 32 publications

(58 citation statements)

References 40 publications

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“…We therefore compared the FIR spectra of parent Au 38 (SC 2 H 4 Ph) 24 and Pd 2 Au 36 (SC 2 H 4 Ph) 24 nanoclusters (Fig. 63 The bands at 217, 285 and 320 cm −1 in both nanoclusters can be assigned to radial, tangential/radial and tangential Au-S modes, respectively. The two spectra are quite similar, showing that the basic structure of the staples is the same in both cases.…”

Section: Resultsmentioning

confidence: 99%

Pd₂Au₃₆(SR)₂₄cluster: structure studies

Bei

Kaziz

et al. 2015

Nanoscale

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The location of the Pd atoms in Pd2Au36(SC2H4Ph)24, is studied both experimentally and theoretically. X-ray photoelectron spectroscopy (XPS) indicates oxidized Pd atoms. Palladium K-edge extended X-ray absorption fine-structure (EXAFS) data clearly show Pd-S bonds, which is supported by far infrared spectroscopy and by comparing theoretical EXAFS spectra in R space and circular dichroism spectra of the staple, surface and core doped structures with experimental spectra.

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Section: Resultsmentioning

confidence: 99%

Pd₂Au₃₆(SR)₂₄cluster: structure studies

Bei

Kaziz

et al. 2015

Nanoscale

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“…[3,4] This opened the way to the development of accuratem ass spectrometry methodologies to assess their stoichiometry. [4] Av ery important role is also played by singlecrystal X-ray crystallography,w hich allowed assessment of the structureo fv arioust hiolate (SR) protected ultrasmall clusters, [4,5] such as the molecular clustert hat will be the subject of the study described herein, Au 25 (SR) 18 . [6][7][8][9][10] Theoretical and experimental efforts have mostlyf ocused on studying aspects directly associated with the core size, structure, and opticalproperties.…”

Section: Introductionmentioning

confidence: 99%

“…[9][10][11][12][13] Insightsi nto the monolayer structure in solution have also been obtained by using IR and Raman vibrational spectroscopy methods. [13][14][15][16][17][18][19] Our recent studies point to electrochemically induced electront ransfer as ap articularly power-ful tool to understand how the clusterc ore interacts with the surrounding mediumt hrough an ot-so-shielding protective monolayer. [12] Historically,t he first clear-cut evidenceo ft he molecule-like properties of some MPCs was, indeed, provided by the observation of as triking core-size-dependent electrochemicalb ehavior.…”

Section: Introductionmentioning

confidence: 99%

Insights into the Interface Between the Electrolytic Solution and the Gold Core in Molecular Au₂₅ Clusters

et al. 2016

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We used a large series of Au25(SCnH2n+1)18 0 clusters (n = 2, 3, 4, 5, 6, 8, 10, 12, 14, 16, 18) to study the effect of n and the presence of electrolytes on their redox potentials. The electrochemical results were analyzed in the framework of concentric capacitor models previously proposed to describe larger monolayer protected clusters. We found that the average dielectric constant of the monolayer εm is significantly larger than that of the ligand chains. The effective value of εm depends on n and is the result of contributions from ligands, solvent and electrolyte. When n increases, εm decreases until a virtually constant value is attained for sufficiently long ligands. The electrochemically calculated HOMO-LUMO energy gap, on the other hand, does not depend on n and, therefore, εm. This energy gap is within error the same as that obtained from the optical spectra of the same clusters.

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“…We previously discussed 15 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 might play a role for the conformation of the ligands, which is not necessarily the same in the dried films and the crystal structure.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

Structural Information on the Au–S Interface of Thiolate-Protected Gold Clusters: A Raman Spectroscopy Study

et al. 2014

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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. Just Accepted "Just Accepted" manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides "Just Accepted" as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. "Just Accepted" manuscripts appear in full in PDF format accompanied by an HTML abstract. "Just Accepted" manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). "Just Accepted" is an optional service offered to authors. Therefore, the "Just Accepted" Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the "Just Accepted" Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these "Just Accepted" manuscripts. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 ...

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Far-infrared spectra of well-defined thiolate-protected gold clusters

Cited by 32 publications

References 40 publications

Pd₂Au₃₆(SR)₂₄cluster: structure studies

Pd₂Au₃₆(SR)₂₄cluster: structure studies

Insights into the Interface Between the Electrolytic Solution and the Gold Core in Molecular Au₂₅ Clusters

Structural Information on the Au–S Interface of Thiolate-Protected Gold Clusters: A Raman Spectroscopy Study

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Far-infrared spectra of well-defined thiolate-protected gold clusters

Cited by 32 publications

References 40 publications

Pd2Au36(SR)24cluster: structure studies

Pd2Au36(SR)24cluster: structure studies

Insights into the Interface Between the Electrolytic Solution and the Gold Core in Molecular Au25 Clusters

Structural Information on the Au–S Interface of Thiolate-Protected Gold Clusters: A Raman Spectroscopy Study

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Pd₂Au₃₆(SR)₂₄cluster: structure studies

Pd₂Au₃₆(SR)₂₄cluster: structure studies

Insights into the Interface Between the Electrolytic Solution and the Gold Core in Molecular Au₂₅ Clusters