Atomically Precise Bimetallic Au19Cu30 Nanocluster with an Icosidodecahedral Cu30 Shell and an Alkynyl–Cu Interface

Wan, Xian‐Kai; Cheng, Xiaoling; Tang, Qing; Han, Ying‐Zi; Hu, Guoxiang; Jiang, De‐en; Wang, Quan‐Ming

doi:10.1021/jacs.7b04622

Cited by 117 publications

(88 citation statements)

References 47 publications

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“…As revealed in a Au 55 Mackay icosahedron (Au 55 ‐MI) and an icosahedral‐based Au 144 nanocluster, there is a Au 42 icosahedron which contains one Au 30 icosidodecahedron and twelve capping Au atoms. A recent report on Au 19 Cu 30 demonstrated an icosidodecahedral Cu 30 shell . We can also recognize an icosidodecahedral Pd 30 shell in a recently determined Mackay icosahedral Pd 55 cluster, whose metallic kernel shares similar structure with Au 55 ‐MI .…”

Section: Figuresupporting

confidence: 66%

“…Besides that, PtAg 42 kernel itself, along with other determined systems such as Au 19 Cu 30 and Pd 55 , provides us a consecutive picture of structural relationship of nanoclusters (Figure S2). An M 43 unit is displayed in cluster 1 and there is no more metal atom in its outer space.…”

Section: Figurementioning

confidence: 99%

“…the door to understanding the alkynyl-gold interface and discoveringm any potential members of this new family of clusters; [25] Zheng et al andW ang et al then prepared severala lkynyl-capped Au-Ag alloyed nanoclusters,i nw hich somei mportant phenomena wereo bserved such as the promoting effects of surface ligands on catalysis by metal nanoparticles, promotion effect of chloride on clusterformation and site preferences in alkynyl-protected multimetallic nanoclusters. [26][27][28][29] In addition, alkynyl-protected Au-Cu alloyedn anoclusters with an icosidodecahedral Cu 30 shell [30] and an alkynyl-Cu interface, and homoleptic alkynyl-protected gold nanoclusters Au 44 [31] and Au 36 [31] have also been reported recently.H owever,r eports of another potential system, alkynyl-stabilized Ag nanoclusters, remain scarce compared with the well-documented gold nanoclusters.S of ar,o nly several alkynyl-protected Ag nanoclusters, e.g.,A g 19 , [32] Ag 25 , [32] Ag 35 , [33] andA g 74 [34] have been structurally determined.…”

mentioning

confidence: 99%

“…preparedaPt-doped [PtAg 24 (SR) 18 ] 2À cluster,w hose structure can be describeda sacentered icosahedral core Pt@Ag 12 stabilized by six distorted dimerics taple -RS-Ag-SR-Ag-SR-motifs, whichw as not observed in un-doped Ag nanoclusters; [36] Bakr et al determinedt he structure of an anisotropic Pt-doped [Pt 2 Ag 23 Cl 7 (PPh 3 ) 10 ]n anocluster, [37] but the structure of its parental hydride-rich [Ag 18 H 16 (PPh 3 ) 10 ] 2 + cluster remains unclear due to its instability. [38] Herein, we report the preparation and structure determination of an alkynyl-protected Pt-doped silver nanocluster with the composition [PtAg 42 (CCC 6 H 4 CH 3 ) 28 ](SbF 6 ) 6 (1).T he cluster, with aP t@Ag 12 @Ag 30 core structure, exhibits the missing icosidodecahedral Ag 30 shell and an M 43 structuralu nit. The interfacial configuration of the metal core-protective shell is also interesting in terms of the protective role of SbF 6 À anions and the direct binding of organic ligands to metal atoms in the sub-shell.…”

mentioning

confidence: 99%

“…After the structurald etermination of 1,i tb ecomesr ational to discuss the icosidodecahedral M 30 shell in detail considering the previously discovered Au 30 ,C u 30 ,a nd Pd 30 icosidodecahedrons. As revealed in aA u 55 Mackay icosahedron (Au 55 -MI) [41] and an icosahedral-based Au 144 nanocluster, [42][43][44] there is aA u 42 icosahedron which contains one Au 30 icosidodecahedron and twelve capping Au atoms.…”

mentioning

confidence: 99%

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An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications

Shen

Mizuta

2017

Chemistry An Asian Journal

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The synthesis and structure determination of an alkynyl-protected Pt-doped Ag superatom nanocluster, [PtAg (C≡CC H CH ) ](SbF ) (1), are reported. The metallic core of this cluster can be viewed as a concentric three-shell Russian doll comprising Pt@Ag @Ag , in which the missing icosidodecahedral Ag shell and a new structural unit, M , have been observed. On the surface of 1, 28 alkynyl groups and 4 SbF anions were found co-protecting it. The protective role of SbF in nanoclusters is unprecedented. Moreover, of the 28 alkynyl ligands, 12 are connected not only with the outermost Ag shell, but also the inner Ag shell through the twelve pentagonal faces of the outermost icosidodecahedral Ag shell. Overall, by determining the crystal structure of 1, we discovered the missing icosidodecahedral Ag shell and the protective effect of SbF anions and demonstrated a novel M structural unit and the unique penetrability of pentagonal faces.

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Section: Figuresupporting

confidence: 66%

Section: Figurementioning

confidence: 99%

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confidence: 99%

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confidence: 99%

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An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications

Shen

Mizuta

2017

Chemistry An Asian Journal

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The Sub‐Nanometer Scale as a New Focus in Nanoscience

2018

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Size is one of the central issues in nanoscience. The practical meaning of the term "sub-nanometric material (SNM)" requires two aspects: (1) its size should be at the atomic level; (2) it shows unique (size-related) properties compared to its nano-counterparts with larger sizes. Here, SNMs in the form of wires (SNWs) and the unique properties arising from their special size are reviewed. First, their polymer-like behavior, including rheological behavior and self-assembly, is dicussed. Their origins may stem from the special size and the ligands around the wire. Even a slight increase in diameter would risk the polymer-like behavior. Meanwhile, the ligands on SNWs are proportional to the inorganic entity at this scale. Consequently, surface ligands should have a profound impact on the properties, like catalysis, self-assembly, optics, etc. To reveal more potential applications, their applications in energy conversion are comprehensively reviewed. To some extent, characterization can greatly influence the way things are observed. Thus, some appropriate characterization techniques are briefly introduced. Finally, another emerging part of SNWs (atomic chain material) is briefly introduced. It is hoped that this review can provide new insights to this special scale.

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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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Atomically Precise Bimetallic Au₁₉Cu₃₀ Nanocluster with an Icosidodecahedral Cu₃₀ Shell and an Alkynyl–Cu Interface

Cited by 117 publications

References 47 publications

An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications

An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications

The Sub‐Nanometer Scale as a New Focus in Nanoscience

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

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Atomically Precise Bimetallic Au19Cu30 Nanocluster with an Icosidodecahedral Cu30 Shell and an Alkynyl–Cu Interface

Cited by 117 publications

References 47 publications

An Atomically Precise Alkynyl‐Protected PtAg42 Superatom Nanocluster and Its Structural Implications

An Atomically Precise Alkynyl‐Protected PtAg42 Superatom Nanocluster and Its Structural Implications

The Sub‐Nanometer Scale as a New Focus in Nanoscience

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

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Atomically Precise Bimetallic Au₁₉Cu₃₀ Nanocluster with an Icosidodecahedral Cu₃₀ Shell and an Alkynyl–Cu Interface

An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications

An Atomically Precise Alkynyl‐Protected PtAg₄₂ Superatom Nanocluster and Its Structural Implications