A Nanocluster [Ag₃₀₇Cl₆₂(SPh^tBu)₁₁₀]: Chloride Intercalation, Specific Electronic State, and Superstability

Abstract

The controlling synthesis of novel nanoclusters of noble metals (Au, Ag) and the determination of their atomically precise structures provide opportunities for investigating their specific properties and applications. Here we report a novel silver nanocluster [Ag307Cl62(SPh t Bu)110] (Ag307) whose structure is determined by X-ray single crystal diffraction. The structure analysis shows that nanocluster Ag307 contains a Ag167 core, a surface shell of [Ag140Cl2S110], and a Cl60 intermediate layer located between Ag167 and [Ag140Cl2S110]. It is a first example that such many chlorides are intercalated into a Ag nanocluster. Chlorides are released in situ from solvent CHCl3. Nanocluster Ag307 exhibits superstability. Differential pulse voltammetry experiment reveals that Ag307 has continuous charging/discharging behavior with a capacitance value of 1.39 aF, while the Ag307 has a surface plasmonic feature. These characteristics show that Ag307 is of metallic behavior. However, its electron paramagnetic resonance (EPR) spectra display a spin magnetic behavior which could be originated from the unpassivated dangling bonds of surface atoms. The direct capture of EPR signals can be attributed to the Cl– intercalating layer which partly suppresses the electronic interactions between core and surface atoms, resulting in the relatively independent electronic states for core and surface atoms.

Ag22 Nanoclusters with Thermally Activated Delayed Fluorescence Protected by Ag/Cyanurate/Phosphine Metallamacrocyclic Monolayers through In‐Situ Ligand Transesterification

“…Finally, it is also worth noting that, the inorganic Cl À in the structure is also probably in-situ generated via the heterolytic cleavage of CÀ Cl bond in CH 2 Cl 2 and such phenomenon was previously often observed in the syntheses of Au or Ag nanoclusters. [20,40,41] Given almost the same geometric structures for these four Ag 22 clusters, hereafter only Ag22-Et was used as the representative to discuss their structures and properties in detail. After workup, the red crystals of Ag22-Et were obtained by slow evaporation of the filtrate (Figure S19).…”

Ag22 Nanoclusters with Thermally Activated Delayed Fluorescence Protected by Ag/Cyanurate/Phosphine Metallamacrocyclic Monolayers through In‐Situ Ligand Transesterification

“…This also underlines the importance of tuning the reaction kinetics by in‐situ ligand formation/derivatization (mainly via transesterification) for more controlled syntheses of metal nanoclusters. Finally, it is also worth noting that, the inorganic Cl − in the structure is also probably in‐situ generated via the heterolytic cleavage of C−Cl bond in CH 2 Cl 2 and such phenomenon was previously often observed in the syntheses of Au or Ag nanoclusters [20, 40, 41] …”

Platonic and Archimedean solids in discrete metal-containing clusters

“…40c); and some clusters (such as Au 133 , 558,559 and Ag 112 545) without a complete regular polyhedral shell. In (AuAg) 267 , the next Mackay overlayer based on the M 55 icosahedron is the first to be crystallographically observed, giving rise to three well-known complete Mackay metal shells of 147 atoms in contrast to the embryonic growth of decahedral (Au 102 , 560 Au 130 , 561 Au 246 , 562 Ag 112 , 545 Ag 136 , 58 Ag 307 , 563 and Ag 374 58 ) and fcc cuboctahedral Au 146 564 and Au 279 60 clusters possessing a partial irregular shell without polyhedral feature. Among the numerous silver-containing metal carbonyl clusters, there are also examples of polyhedral features, such as [Ag 16 Ni 24 (CO) 40 ] 4À (Ag 16 Ni 24 , Fig.…”