[Ag15(N-triphos)4(Cl4)](NO3)3: a stable Ag–P superatom with eight electrons (N-triphos = tris((diphenylphosphino)methyl)amine)

Shen, Xue-Tao; Ma, Xue-Li; Ni, Qing-Ling; Ma, Meng-Xia; Gui, Liu-Cheng; Hou, Cheng; Hou, Ruobing; Wang, Xiu-Jian

doi:10.1039/c7nr07308a

Cited by 27 publications

(12 citation statements)

References 49 publications

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“…From top left to bottom right: Chiral phosphine/thiolate coprotected Ag and Ag-based bimetallic NCs: [Ag 15 (TP) 4 Cl 4 ] 3+ , [239] Ag 16 (SR) 14 (DPPE) 4 , [238] Ag 23 (SR) 18 (PPh 3 ) 8 , [240] [Au 1 Ag 24 (SR) 17 (DPPM) 3 ] 2+ , [241] Pt 1 Ag 28 (SR) 18 (PPh 3 ) 4 , [242] Ag 29 (SR) 12 (PPh 3 ) 4 , [221] [Ag 32 (SR) 24 (DPPE) 5 ] 2− , [238] [Ag 32 (SR) 13 (DPPM) 5 Cl 8 ] 3+ , [243] Ag 33 (SR) 24 (PPh 3 ) 4 , [244] Ag 43 (SR) 25 (PPh 3 ) 4 , [245] [Ag 45 (SR) 16 (DPPM) 4 Br 12 ] 3+ , [243] Au 9 Ag 36 -(SR) 27 (PPh 3 ) 6 , [246] [Ag 67 (SR) 32 (PPh 3 ) 8 ] 3+ , [247] Ag 78 (SR) 42 (DPPP) 6 . [248] Achiral phosphine/thiolate coprotected Ag NCs: Ag 14 (SR) 12 -(PPh 3 ) 8 , [249] Pt 1 Ag 26 (SR) 18 (PPh 3 ) 6 , [250] Ag 38 (SR) 26 (PPh 3 ) 8 , [251] Ag 46 (SR) 24 (PPh 3 ) 8 , [245,252] Ag 50 (SR) 30 (DPPM) 6 , [253] Ag 63 (SR) 36 (PPh 3 ) 8 .…”

Section: Thiolate/phosphine Coprotected Ag Ncsmentioning

confidence: 99%

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

et al. 2020

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In chemical science, chirality is indeed one of the most extensively studied phenomena. A chiral molecule possesses a pair of enantiomers and sometimes, only one of the enantiomers is effective as a functional unit or drug. [1,2] The mechanism on how the notorious enantiomers of thalidomide lead to teratogenic newborns has been revealed recently. [3] Chirality in coordination complexes has also been generalized in detail. [4] A classic example of molecules with point chirality is that it contains an asymmetric sp 3 carbon atom which is attached with four different atoms or groups. Such a molecule is not superimposable with its mirror image, and for a simple coordination complex, a metal atom-which is at the centerserves as the role of the chiral carbon (i.e., point chirality). As a result, the relative spatial arrangement of the substituents gives either a clockwise or an anticlockwise order, corresponding to the R and S enantiomers. Of note, the R/S notation of chirality has no fixed relation to the d/l notation (for sugars and amino acids). More generally speaking, chiral object is lack of S n symmetry elements; in other words, if a mirror plane (σ) and inversion (i) are both missing in the object, then it becomes chiral. From this definition, irregular objects are all chiral. Objects of C n (with n-fold axis) or D n (with C 2 axis perpendicular to the n-fold axis) symmetry are much more appealing as long-range order is created. Along with organic chiral molecules, [2] chiral complexes, [4] and chiral supramolecular systems with autonomous self-assembly generated by intermolecular noncovalent interactions have been discussed thoroughly in previous reviews. [5-9] Chiral inorganic nanostructures, with intermediate sizes between molecules of Å and objects of micrometers, are of critical significance owing to their tremendous applications in chiral catalysis, chiroptical metamaterials, enantioseparation, biomolecular and enantiomer sensing, as well as medicine. [10-12] For chiral semiconductor nanoparticles (NPs), commonly called quantum dots (QDs), such as cadmium chalcogenides, the chiral surface ligands are attached onto the QDs through covalent bonds, [13-17] and many applications can be designed. [18] The interactions of chiral moieties attached on graphene NPs lead to their helical assembly, enriching the optical and electronic properties of these chiral nanostructures and facilitating their applications. [19-21] The studies on chiral metal NPs greatly overwhelm those on the semiconductor counterparts. Metal NPs are known to have Chirality is ubiquitous in nature and occurs at all length scales. The development of applications for chiral nanostructures is rising rapidly. With the recent achievements of atomically precise nanochemistry, total structures of ligand-protected Au and other metal nanoclusters (NCs) are successfully obtained, and the origins of chirality are discovered to be associated with different parts of the cluster, including the surface ligands (e.g., swirl patterns), the organic-inorganic in...

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Section: Thiolate/phosphine Coprotected Ag Ncsmentioning

confidence: 99%

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

et al. 2020

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“…a vertex‐sharing bi‐decahedra) or the assembled icosahedral core are widely found in Ag clusters such as Ag 20 , Ag 21 , Ag 25 , Ag 29 , Ag 32–35 , Ag 45 , and Ag 74 , as well as the ino‐decahedral core unit of Ag 48 . FCC‐based (FCC=face centered cubic) core structures are also known in clusters of Ag 14 , Ag 15 , Ag 23 , Ag 38 , Ag 46 , Ag 62 , Ag 63 , and Ag 67 …”

Section: Figurementioning

confidence: 99%

Rhombicuboctahedral Ag₁₀₀: Four‐Layered Octahedral Silver Nanocluster Adopting the Russian Nesting Doll Model

Bai

Song

et al. 2020

Angewandte Chemie

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Precise atomic structure of metal nanoclusters (NCs) is fundamental for elucidating the structure–property relationships and the inherent size‐evolution principles. Reported here is the largest known FCC‐based (FCC=face centered cubic) silver nanocluster, [Ag100(SC6H33,4F2)48(PPh3)8]−: the first all‐octahedral symmetric nesting Ag nanocluster with a four‐layered Ag6@Ag38@Ag48S24@Ag8S24P8 structure, consistent symmetry elements, and a unique rhombicuboctahedral morphology distinct from theoretical predictions and previously reported FCC‐based Ag clusters. DFT studies revealed extensive interlayer interactions and degenerate frontier orbitals. The FCC‐based Russian nesting doll model constitutes a new platform for the study of the size‐evolution principles of Ag NCs.

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“…Normally, these nanoclusters are composed of core–shell structures stabilized by surface reagents which are usually used as thiolate, phosphine, alkyne, or their mixture. ,, The totally determined structure can provide information on not only the atom-precise core structure but also the surface shell structure and the interfacial bonding between core and surface structure. The reported nanoclusters exhibit a broad range of structural forms, including face-centered cubic (fcc), hexagonally close-packed (hcp), icosahedral, and decahedral structures.…”

Section: Introductionmentioning

confidence: 99%

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

Liang

et al. 2021

J. Am. Chem. Soc.

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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.

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[Ag₁₅(N-triphos)₄(Cl₄)](NO₃)₃: a stable Ag–P superatom with eight electrons (N-triphos = tris((diphenylphosphino)methyl)amine)

Cited by 27 publications

References 49 publications

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Rhombicuboctahedral Ag₁₀₀: Four‐Layered Octahedral Silver Nanocluster Adopting the Russian Nesting Doll Model

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

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[Ag15(N-triphos)4(Cl4)](NO3)3: a stable Ag–P superatom with eight electrons (N-triphos = tris((diphenylphosphino)methyl)amine)

Cited by 27 publications

References 49 publications

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Rhombicuboctahedral Ag100: Four‐Layered Octahedral Silver Nanocluster Adopting the Russian Nesting Doll Model

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

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[Ag₁₅(N-triphos)₄(Cl₄)](NO₃)₃: a stable Ag–P superatom with eight electrons (N-triphos = tris((diphenylphosphino)methyl)amine)

Rhombicuboctahedral Ag₁₀₀: Four‐Layered Octahedral Silver Nanocluster Adopting the Russian Nesting Doll Model

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