Stabilizing subnanometer Ag(0) nanoclusters by thiolate and diphosphine ligands and their crystal structures

Yang, Huayan; Wang, Yu; Zheng, Nanfeng

doi:10.1039/c3nr34328f

Cited by 156 publications

(172 citation statements)

References 34 publications

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“…The occupied Mn(3d) states are somewhat hybridized with the surrounding silver (or gold) d states but hold still the majority of the localized spin moment at the Mn atom. Our calculations are in line with previous work predicting magnetic properties for Mn-doped MnAu 24 (SR) 18 clusters. 34−36…”

Section: ■ Results and Discussionsupporting

confidence: 90%

Theoretical Analysis of the M₁₂Ag₃₂(SR)₄₀^4– and X@M₁₂Ag₃₂(SR)₃₀^4– Nanoclusters (M = Au, Ag; X = H, Mn)

Gell

Häkkinen

2014

J. Phys. Chem. C

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We analyze the electronic structure and optical properties of the recently reported, structurally known M 12 Ag 32 (SR) 30 4− clusters (M = Au, Ag) by using density functional theory and time-dependent density functional perturbation theory. Effects of the chemical changes in the metal core, charge of the cluster, and nature of the thiolate ligand on the electronic structure and optical absorption are reported. In addition, doping the metal core with a magnetic transition metal atom (Mn) or hydrogen (protons) is discussed. Although all these clusters can be considered as 18-electron superatoms with a shell configuration 1S 2 1P 6 1D 10 , we find that the optical spectrum is sensitive to the charge state and chemical composition of the core and that all optical transitions in the visible range have important contributions from the electron-rich aromatic ligands. Added protons work as counter-cations reducing the overall charge but keeping the stable 18-electron configuration. Finally, our calculations predict that doping the center hole of the metal core by a manganese atom makes the cluster a 20-electron superatom with a configuration 1S 2 1P 6 1D 10 2S 2 but keeps the maximal spinmoment localized at the dopant in a Mn(3d 5 ) configuration by the Hund rule.

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Section: ■ Results and Discussionsupporting

confidence: 90%

Theoretical Analysis of the M₁₂Ag₃₂(SR)₄₀^4– and X@M₁₂Ag₃₂(SR)₃₀^4– Nanoclusters (M = Au, Ag; X = H, Mn)

Gell

Häkkinen

2014

J. Phys. Chem. C

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“…From the crystal data, an Ag 8 core was initially assigned. 32 However, as seen from Figure S2 (Supporting Information), the S-symmetric HOMO is localized mainly on the two-layer Ag 6 part that contains a planar rhombus capped by two atoms (Figure 1b). On the basis of this analysis we assign this geometrical unit as the metal core.…”

Section: ■ Results and Discussionmentioning

confidence: 95%

“…This structure was described initially as having a low-symmetry Ag 8 core with a nominal charge of 6+. 32 Our analysis on the electronic states (discussed below) will show that the core is best described as Ag 6 with a nominal charge of 4+, a planar four-atom rhombus capped below by two additional silver atoms, as shown in Figure 1b. Though clusters 1 and 2 are of 8 (2) clusters.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Superatomic S² Silver Clusters Stabilized by a Thiolate–Phosphine Monolayer: Insight into Electronic and Optical Properties of Ag₁₄(SC₆H₃F₂)₁₂(PPh₃)₈ and Ag₁₆(SC₆H₃F₂)₁₄(DPPE)₄

2014

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The electronic structure of two recently crystallographically solved, thiolate-phosphine protected silver clusters Ag14 and Ag16 are analyzed via density functional theory (DFT) and their optical excitations are analyzed from time-dependent DFT perturbation theory. Both clusters can be characterized as having the S(2) free-electron configuration in the metal core, which is the first time such a configuration is confirmed for structurally known ligand-protected noble metal clusters. However, their different core shapes and ligand layer induce significantly different optical spectra. Performance of gradient-corrected DFT functionals is discussed and it is shown that the asymptotically correct Leeuwen-Baerends LB94 functional reproduces the optical spectrum of Ag14 in a good agreement with experiment. Choice of the functional becomes important for clusters where the optical transitions are dominated by the electron-rich ligand layer.

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“…For example, the stable Au 25 (SR) 18 cluster shows a fragment in the mass spectrum due to the Au 4 (SR) 4 loss. 52 Even the stable Ag 44 (SR) 30 cluster, for which the crystal structure was determined recently, 35,36 shows several fragments due to Ag m (SR) n losses. 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).…”

Section: Section: Physical Processes In Nanomaterials and Nanostructuresmentioning

confidence: 99%

“…However, recent crystal structures of silver clusters (such as [Ag 14 53 suggest that such ligand-excess Figure 3. MS/MS data of m/z 2839.…”

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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Stabilizing subnanometer Ag(0) nanoclusters by thiolate and diphosphine ligands and their crystal structures

Cited by 156 publications

References 34 publications

Theoretical Analysis of the M₁₂Ag₃₂(SR)₄₀^4– and X@M₁₂Ag₃₂(SR)₃₀^4– Nanoclusters (M = Au, Ag; X = H, Mn)

Theoretical Analysis of the M₁₂Ag₃₂(SR)₄₀^4– and X@M₁₂Ag₃₂(SR)₃₀^4– Nanoclusters (M = Au, Ag; X = H, Mn)

Superatomic S² Silver Clusters Stabilized by a Thiolate–Phosphine Monolayer: Insight into Electronic and Optical Properties of Ag₁₄(SC₆H₃F₂)₁₂(PPh₃)₈ and Ag₁₆(SC₆H₃F₂)₁₄(DPPE)₄

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

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Stabilizing subnanometer Ag(0) nanoclusters by thiolate and diphosphine ligands and their crystal structures

Cited by 156 publications

References 34 publications

Theoretical Analysis of the M12Ag32(SR)404– and X@M12Ag32(SR)304– Nanoclusters (M = Au, Ag; X = H, Mn)

Theoretical Analysis of the M12Ag32(SR)404– and X@M12Ag32(SR)304– Nanoclusters (M = Au, Ag; X = H, Mn)

Superatomic S2 Silver Clusters Stabilized by a Thiolate–Phosphine Monolayer: Insight into Electronic and Optical Properties of Ag14(SC6H3F2)12(PPh3)8 and Ag16(SC6H3F2)14(DPPE)4

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

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Theoretical Analysis of the M₁₂Ag₃₂(SR)₄₀^4– and X@M₁₂Ag₃₂(SR)₃₀^4– Nanoclusters (M = Au, Ag; X = H, Mn)

Theoretical Analysis of the M₁₂Ag₃₂(SR)₄₀^4– and X@M₁₂Ag₃₂(SR)₃₀^4– Nanoclusters (M = Au, Ag; X = H, Mn)

Superatomic S² Silver Clusters Stabilized by a Thiolate–Phosphine Monolayer: Insight into Electronic and Optical Properties of Ag₁₄(SC₆H₃F₂)₁₂(PPh₃)₈ and Ag₁₆(SC₆H₃F₂)₁₄(DPPE)₄