Ag44(SR)304−: a silver–thiolate superatom complex

Harkness, Kellen M.; Tang, Yanjun; Dass, Amala; Pan, Jun; Kothalawala, Nuwan; Reddy, Vijay J.; Cliffel, David E.; Demeler, Borries; Stellacci, Francesco; Bakr, Osman M.; McLean, John A.

doi:10.1039/c2nr30773a

Cited by 158 publications

(211 citation statements)

References 74 publications

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“…It is important to mention here that for this cluster the molecular peak with 4− charge has much lower intensity compared with the fragments seen in the lower mass range (m/z 100−1500). 32 Au 25 and Ag 44 are the most stable clusters reported so far, for the case of gold and silver, respectively. They have closed-shell electronic configuration consisting of 8 and 18 number of electrons.…”

Section: Section: Physical Processes In Nanomaterials and Nanostructuresmentioning

confidence: 99%

Isolation and Tandem Mass Spectrometric Identification of a Stable Monolayer Protected Silver–Palladium Alloy Cluster

Sarkar

Chakraborty

Panwar

et al. 2014

J. Phys. Chem. Lett.

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A selenolate-protected Ag−Pd alloy cluster was synthesized using a one-pot solution-phase route. The crude product upon chromatographic analyses under optimized conditions gave three distinct clusters with unique optical features. One of these exhibits a molecular peak centered at m/z 2839, in its negative ion mass spectrum assigned to Ag 5 Pd 4 (SePh) 12 − , having an exact match with the corresponding calculated spectrum. Tandem mass spectrometry of the molecular ion peak up to MS 9 was performed. Complex isotope distributions in each of the mass peaks confirmed the alloy composition. We find the Ag 3 Pd 3 − core to be highly stable. The composition was further supported by scanning electron microscopy, energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy. SECTION: Physical Processes in Nanomaterials and

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Section: Section: Physical Processes In Nanomaterials and Nanostructuresmentioning

confidence: 99%

Isolation and Tandem Mass Spectrometric Identification of a Stable Monolayer Protected Silver–Palladium Alloy Cluster

Sarkar

Chakraborty

Panwar

et al. 2014

J. Phys. Chem. Lett.

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“…3+ NC. Figure S7 shows the 31 P NMR peaks of the clusters in comparison to 31 P NMR peak of free PPh3. A broad peak of the cluster at 8.1 ppm is due to the phosphine bound to the cluster, while a sharp peak at 27.4 ppm could be due to free triphenylphosphine oxide (PPh3O), probably resulted from the oxidation of free PPh3 (if anything left in the solution during washing steps).…”

Section: Synthesis Purification and Crystallizationmentioning

confidence: 99%

“…Nevertheless, the number of stable atomically monodisperse thiolate-protected silver NCs is rising, having attracted much research attention with the hope of utilizing them as a viable and cheaper alternative to gold. [25][26][27][28][29][30][31][32][33][34] A key challenge remaining for silver NCs is obtaining highly anisotropic shapes. In gold, NCs of anisotropic shapes were reported through solely thiols 35,36 and co-ligands of phosphines and thiols 37,38 .…”

Section: Introductionmentioning

confidence: 99%

[Ag₆₇(SPhMe₂)₃₂(PPh₃)₈]³⁺: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

Alhilaly¹,

Bootharaju²,

Joshi³

et al. 2016

J. Am. Chem. Soc.

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174

134

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Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag67(SPhMe2)32(PPh3)8]3+. The crystal structure shows an Ag23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag23 core was formed through an unprecedented centered cuboctahedron, i.e., Ag13, unlike the common centered Ag13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag67(SPhMe2)32(PPh3)8]3+ and a reduced model [Ag67(SH)32(PH3)8]3+. The lowest metal-to-metal transitions in the range 500–800 nm could be explained by considering the reduced model that shows almost identical electronic states to 32 free electrons in a jellium box. The successful synthesis of the large box-shaped Ag67 NC facilitated by the combined use of phosphine and thiol paves the way for synthesizing other metal clusters with unprecedented shapes by judicious choice of thiols and phosphines.

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“…[1][2][3][4][5][6][7] (p-MBA) 44 ]. 12,13 Intermetallic Au m Ag n and Au m Cu n nanoclusters are also isolable.…”

Section: Introductionmentioning

confidence: 99%

A Cu₂₅ Nanocluster with Partial Cu(0) Character

et al. 2015

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Atomically precise copper nanoclusters (NCs) are of immense interest for a variety of applications, but have remained elusive. Herein we report the isolation of a copper NC, [Cu 25 H 22 (PPh 3 ) 12 ]Cl (1), from the reaction of Cu(OAc) and CuCl with Ph 2 SiH 2 , in the presence of PPh 3 . Complex 1 has been fully characterized, including analysis by X-ray crystallography, XANES, and XPS. In the solid state, complex 1 is constructed around a Cu 13 centered-icosahedron and formally features partial Cu(0) character. XANES of 1 reveals a Cu K-edge at 8979.6 eV, intermediate between the edge energies of Cu (0) and Cu(I), confirming our oxidation state assignment. This assignment is further corroborated by determination of the Auger parameter for 1, which also falls between those recorded for Cu(0) and Cu(I).

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Ag44(SR)304−: a silver–thiolate superatom complex

Cited by 158 publications

References 74 publications

Isolation and Tandem Mass Spectrometric Identification of a Stable Monolayer Protected Silver–Palladium Alloy Cluster

Isolation and Tandem Mass Spectrometric Identification of a Stable Monolayer Protected Silver–Palladium Alloy Cluster

[Ag₆₇(SPhMe₂)₃₂(PPh₃)₈]³⁺: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

A Cu₂₅ Nanocluster with Partial Cu(0) Character

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Ag44(SR)304−: a silver–thiolate superatom complex

Cited by 158 publications

References 74 publications

Isolation and Tandem Mass Spectrometric Identification of a Stable Monolayer Protected Silver–Palladium Alloy Cluster

Isolation and Tandem Mass Spectrometric Identification of a Stable Monolayer Protected Silver–Palladium Alloy Cluster

[Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

A Cu25 Nanocluster with Partial Cu(0) Character

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[Ag₆₇(SPhMe₂)₃₂(PPh₃)₈]³⁺: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

A Cu₂₅ Nanocluster with Partial Cu(0) Character