Site-specific sulfur-for-metal replacement in a silver nanocluster

Wu, Ya-Ge; Huang, Jiann‐Wen; Zhang, Chong; Guo, Xin; Wu, Wei-Na; Dong, Xi‐Yan; Zang, Shuang‐Quan

doi:10.1039/d2cc00794k

“…The spectra explicitly indicate the presence of both Pd and Ag in ratios similar to the expected molecular composition. Furthermore, the spectra indicate the oxidation state of Pd to be zero and the Ag approaching Ag(I) for 1 – 3 , Figure S13 [29] …”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, the spectra indicate the oxidation state of Pd to be zero and the Ag approaching Ag(I) for 1-3, Figure S13. [29] The hydride provides a unique probe for configuration changes in the metallic framework due to the coupling with its surrounding silver atoms. The integration ratios of the 1 H NMR Scheme 1.…”

Section: Synthesis and Reactivitymentioning

confidence: 99%

Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters

Ni

¹

,

Pillay

²

,

Chiu

³

et al. 2023

Chemistry A European J

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The first 8-electron Pd/Ag superatomic alloys with an interstitial hydride [PdHAg 19 (dtp) 12 ] (dtp = S 2 P(O i Pr) 2 À ) 1 and [PdHAg 20 (dtp) 12 ] + 2 are reported. The targeted addition of a single Ag atom to 1 is achieved by the reaction of one equivalent of trifluoroacetic acid, resulting in the formation of 2 in 55 % yield. Further modification of the shell results in the formation of [PdAg 21 (dtp) 12 ] + 3 via an internal redox reaction, with the system retaining an 8-electron superatomic configuration. The interstitial hydride in 1 and 2 contributes its 1s 1 electron to the superatomic electron count and occupies a PdAg 3 tetrahedron. The distributions of isomers corresponding to different dispositions of the outer capping Ag atoms are investigated by multinuclear VT NMR spectroscopy. The emissive state of 3 has a lifetime of 200 μs (λ ex = 448; λ em = 842), while 1 and 2 are non-emissive. The catalytic reduction of 4-nitrophenol is demonstrated with 1-3 at room temperature.

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Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry

Dong

¹

,

Huang

²

,

Sagadevan

³

et al. 2023

Angewandte Chemie

0

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Elucidating single‐atom effects on the fundamental properties of nanoparticles is challenging because single‐atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu58H20PET36(PPh3)4]2+ (Cu58; PET: phenylethanethiolate; PPh3: triphenylphosphine) nanocluster—an atomically precise nanoparticle—that can be transformed into the surface‐defective analog [Cu57H20PET36(PPh3)4]+ (Cu57). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu57. Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu58, Cu57 shows promising activity for click chemistry, particularly photoinduced [3+2] azide‐alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu57 after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single‐surface atom modification on nanoparticle properties but also showcases single‐atom surface modification as a powerful means for designing nanoparticle catalysts.

show abstract

Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry

Dong

¹

,

Huang

²

,

Sagadevan

³

et al. 2023

View full text Add to dashboard Cite

Elucidating single‐atom effects on the fundamental properties of nanoparticles is challenging because single‐atom modifications are typically accompanied by appreciable changes to the overall particle's structure. Herein, we report the synthesis of a [Cu58H20PET36(PPh3)4]2+ (Cu58; PET: phenylethanethiolate; PPh3: triphenylphosphine) nanocluster—an atomically precise nanoparticle—that can be transformed into the surface‐defective analog [Cu57H20PET36(PPh3)4]+ (Cu57). Both nanoclusters are virtually identical, with five concentric metal shells, save for one missing surface copper atom in Cu57. Remarkably, the loss of this single surface atom drastically alters the reactivity of the nanocluster. In contrast to Cu58, Cu57 shows promising activity for click chemistry, particularly photoinduced [3+2] azide‐alkyne cycloaddition (AAC), which is attributed to the active catalytic site in Cu57 after the removal of one surface copper atom. Our study not only presents a unique system for uncovering the effect of a single‐surface atom modification on nanoparticle properties but also showcases single‐atom surface modification as a powerful means for designing nanoparticle catalysts.

show abstract

Site-specific sulfur-for-metal replacement in a silver nanocluster

Abstract: A new Ag36 nanocluster with a closed electronic structure and eight valence electrons is reported, which has a similar structure to an open-shell Ag34 nanocluster with three valence electrons, except...

Cited by 5 publications

References 57 publications

Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters

Controlled Shell and Kernel Modifications of Atomically Precise Pd/Ag Superatomic Nanoclusters

Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry

Isostructural Nanocluster Manipulation Reveals Pivotal Role of One Surface Atom in Click Chemistry

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