Generation of Small Gold Clusters with Unique Geometries through Cluster‐to‐Cluster Transformations: Octanuclear Clusters with Edge‐sharing Gold Tetrahedron Motifs

Kamei, Yoshihiko; Shichibu, Yukatsu; Konishi, Katsuaki

doi:10.1002/ange.201102901

Cited by 35 publications

(30 citation statements)

References 28 publications

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“…Noble metal nanoparticles 1 − 9 have received significant attention in recent decades due to their unique electronic properties that make them interesting for a wide range of applications, 10 − 16 in particular, sensing 10 , 12 and catalysis. 13 , 16 If the number of atoms is small, these particles are highly symmetric and exhibit a significant energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).…”

Section: Introductionmentioning

confidence: 99%

Not Completely Innocent: How Argon Binding Perturbs Cationic Copper Clusters

et al. 2020

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Argon is often considered as an innocent probe that can be attached and detached to study the structure of a particular species without perturbing the species too much. We have investigated whether this assumption also holds for small copper cationic clusters and demonstrated that small but significant charge transfer from argon to metal changes the remaining binding positions, leading in general, to weaker binding of other argon atoms. The exception is binding to just one copper ion, where the binding of the first argon facilitates the binding of the second.

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Section: Introductionmentioning

confidence: 99%

Not Completely Innocent: How Argon Binding Perturbs Cationic Copper Clusters

et al. 2020

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“…Electrospray ionization mass spectrometry (ESI/MS) has proven to be valuable in monitoring the solution-phase growth [3,4] of coinage metal nanoclusters and to direct their bulk synthesis [3r] as well as to monitor their solution and gas phase reactivity [3,5]. For example, these MS studies have revealed that the growth of bis-phosphine capped gold nanoclusters, upon reduction of Au(I) salts by sodium borohydride, is complex and depends on a range of factors including: (i) the solvent(s), (ii) the type of reductant, (iii) the gold salt, (iv) the steric and geometric constraints of the bis-phosphine and, (v) the molar ratio of the Au(I) salt to the bis-phosphine.…”

Section: Introductionmentioning

confidence: 99%

Bis(dimethylphosphino)methane-ligated silver chloride, cyanide and hydride cluster cations: Synthesis and gas-phase unimolecular reactivity

Clark

Zavras

Khairallah

et al. 2015

International Journal of Mass Spectrometry

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Dedicated to Prof Ronnie Bierbaum on the occasion of her 65th Birthday and in recognition of her important contributions to Gas-phase Ion Chemistry and service to the American Society for Mass Spectrometry. Keywords:Ligand-protected silver hydride clusters Bis-phosphine Me 2 P(CH 2 )PMe 2 Collision-induced dissociation Electron-induced dissociation DFT calculations A B S T R A C T Electrospray ionization mass spectrometry (ESI/MS) of mixtures of AgNO 3 or AgBF 4 with the capping ligand Me 2 PÀ À(CH 2 )À ÀPMe 2 (dmpm, L) in a solution of 1:1 methanol:chloroform or acetonitrile revealed the formation of: dinuclear clusters [Ag 2 L 2 ] 2+ , [Ag 2 (LÀ ÀH)L] + , and [Ag 2 ClL 2 ] + ; trinuclear clusters primarily as [Ag 3 Cl 2 L 3 ] + ; and the tetranuclear cluster [Ag 4 Cl 3 L 3 ] + . Addition of NaBH 4 to these solutions of dmpmprotected clusters results in the formation of the silver hydride cluster cations [Ag 2 HL 2 ] + , [Ag 3 HL 3 ] 2+ , [Ag 3 HL 4 ] 2+ , [Ag 3 H(CN)L 3 ] + and [Ag 3 HClL 3 ] + as determined by ESI/MS. Use of NaBD 4 confirmed that the borohydride is the source of the hydride in these clusters. The gas-phase unimolecular chemistry of selected clusters was examined in a LTQ-FT hybrid linear ion trap (LIT) mass spectrometer. Low-energy collision-induced dissociation (CID) was performed on the clusters [Ag 3 Cl 2 L 3 ] + , [Ag 3 HClL 3 ] + , [Ag 3 H(CN)L 3 ] + , [Ag 3 HL 3 ] 2+ , [Ag 3 HL 4 ] 2+ and their nascent fragments. Neutral ligand loss, core fission and ligand activation were observed to depend on the cluster stoichiometry. Thus, [Ag 3 XYL 3 ] + (X, Y = Cl; X = H; Y = Cl or CN) mainly fragment via ligand loss, [Ag 3 XYL 2 ] + undergoes both ligand loss and core fission, [Ag 3 XYL] + undergoes core fission and [Ag 2 YL] + undergoes ligand activation. Small yields of reductive elimination of HY are observed for [Ag 3 HYL 2 ] + (Y = Cl and CN). Density functional theory (DFT) calculations were used to calculate the energetics of the optimised structures for all parent, fragment ions and neutrals and to estimate the reaction endothermicities.Generally there is a reasonable agreement between the most abundant product ion formed and the predicted endothermicity, except for the reductive elimination reactions. Finally, electron-induced dissociation (EID) of [Ag 3 HL 3 ] 2+ and [Ag 3 HL 4 ] 2+ gave similar fragmentation channels to CID.

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“…Clusters with 8 gold atoms, in contrast, tend to adopt rather less symmetric structures, such as the 'core + exo' geometries of [Au 8 (dppp) 4 ] 2+ and [Au 8 (dppp) 4 X 2 ] 2+ , X=Cl − , PhC≡C − (Fig. 1) where an octahedral Au 6 core is capped by two 'exo' gold atoms 14,15 , or the highly distorted cube reported recently for [Au 8 (PPh 3 ) 8 ] 2+ 13 .…”

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confidence: 99%

A family of lead clusters with precious metal cores

et al. 2020

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Gold nanoparticles have been used for centuries, both for decoration and in medical applications. More recently, many of the major advances in cluster chemistry have involved welldefined clusters containing tens or hundreds of atoms, either with or without a ligand shell. In this paper we report the synthesis of two gold/lead clusters, [Au 8 Pb 33 ] 6− and [Au 12 Pb 44 ] 8− , both of which contain nido [Au@Pb 11 ] 3− icosahedra surrounding a core of Au atoms. Analogues of these large clusters are not found in the corresponding Ag chemistry: instead, the Ag-centered nido icosahedron, [Ag@Pb 11 ] 3− , is the only isolated product. The structural chemistry, along with the mass spectrometry which shows the existence of [Au 2 Pb 11 ] 2− but not [Ag 2 Pb 11 ] 2− , leads us to propose that the former species is the key intermediate in the growth of the larger clusters. Density functional theory indicates that secondary π-type interactions between the [Au@Pb 11 ] 3− ligands and the gold core play a significant part in stabilizing the larger clusters.

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Generation of Small Gold Clusters with Unique Geometries through Cluster‐to‐Cluster Transformations: Octanuclear Clusters with Edge‐sharing Gold Tetrahedron Motifs

Cited by 35 publications

References 28 publications

Not Completely Innocent: How Argon Binding Perturbs Cationic Copper Clusters

Not Completely Innocent: How Argon Binding Perturbs Cationic Copper Clusters

Bis(dimethylphosphino)methane-ligated silver chloride, cyanide and hydride cluster cations: Synthesis and gas-phase unimolecular reactivity

A family of lead clusters with precious metal cores

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