Total Structure Determination of Au16(S-Adm)12 and Cd1Au14(StBu)12 and Implications for the Structure of Au15(SR)13

Yang, Sha; Chen, Shuang; Xiong, Lin; Liu, Chong; Yu, Haizhu; Wang, Shuxin; Rosi, Nathaniel L.; Pei, Yong; Zhu, Manzhou

doi:10.1021/jacs.8b04257

Cited by 83 publications

(108 citation statements)

References 55 publications

(60 reference statements)

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“…From top left to bottom right: Chiral Au-thiolate NCs: Au 16 (SAdm) 12 , [177] Au 20 (TBBT) 16 , [58] Au 21 (StBu) 15 , [173] Au 24 (SAdm) 16 , [169] Au 24 (SePh) 20 , [163] Au 28 (TBBT) 20 , [127] Au 28 (S-c-C 6 H 11 ) 20 , [178] Au 30 (StBu) 18 , [141] Au 34 (S-c-C 6 H 11 ) 22 , [179] Au 38 (PET) 24 -Q, [99] Au 40 (o-MBT) 24 , [123] Au 42 (S-c-C 6 H 11 ) 26 , [179] Au 42 (TBBT) 26 -F, [180] Au 42 (TBBT) 26 -N, [181] Au 43 (S-c-C 6 H 11 ) 25 , [182] Au 44 (2,4-DMBT) 26 , [124] Au 44 (TBBT) 28 , [138] Au 48 (TBBT) 28 , [183] Au 49 (2,4-DMBT) 27 , [184] Au 52 (TBBT) 32 , [123] Au 60 S 6 (SCH 2 Ph) 36 , [144] Au 92 (TBBT) 44 , [136] Au 102 (p-MBA) 44 , [59] Au 103 S 2 (S-Nap) 41 , [118] Au 130 (p-MBT) 50 , [117] Au 133 (TBBT) 52 , [98] Au 144 (SCH 2 Ph) 60 , [100] Au 146 (p-MBA) 57 , [185] Au 246 (p-MBT) 80 , [60] Au 279 (TBBT) 84 . [186,187] Achiral Au-thiolate NCs: Au 18 (S-c-C 6 H 11 ) 14 , [130] Au 21 (SAdm) 15 , [131] [Au 23 (S-c-C 6 H 11 ) 16 ] − , [188] Au 24 (TBBM) 20 , [128] [Au 25 (PET) 18 ] − , [80] Au 30 (SAdm) 18 , [174] Au 36 (TBBM) 8 Cl 20 , [189] Au 38 S 2 (SAdm) 20 , [142] Au 52 (PET) 32 .…”

Section: Achiral/chiral Au-sr 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: Achiral/chiral Au-sr Ncsmentioning

confidence: 99%

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

et al. 2020

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“…Furthermore, DFT calculations indicatet hat [Ag 13 ] 5 + can be treated as an 8e À superatomic unit (with 1S 2 1P 6 closed-shell configuration) capped by ae xternal shell ( Figure 5B,r ight). [33] Many dichalcogenolated silver superatomic nanoclusters based on [Ag 21 {S 2 P(OiPr) 2 } 12 ] + ,t hrough ligand and doping engineering, such as [Ag 21 {Se 2 P(OEt) 2 } 12 ] + , [Ag 20 {S 2 P i (OR) 2 [34][35][36][37] were obtaineda nd summarized in detail by the group of Liu in a review on copper/silver superatomic nanoclusters. [61] With more in-depth research,t he exploration of gold ands ilver nanocluster analogues has attracted attention to understand fundamental differences.…”

Section: Metal Superatomiccluster Containing M 13 Units Capped With Tmentioning

confidence: 99%

“…Metal nanoclusters, as ab ridge between metal complexesa nd nanoparticles, are attracting great interest, owing to their welldetermined structures and promising properties, such as catalysis, sensing, chirality,a nd photoluminescence, which are available for fundamental research and applications. [1][2][3][4][5][6] Also, these types of nanoclustersa re considered to be ideal modelst oi nvestigate structure-property correlations. [7][8][9][10][11][12] As one type of metal nanoclusters, metal superatomic clusters presente lectronic structures similar withone certaina tom from the periodic table, and the electronic characteristic can be maintained during assembly with other atoms and/or clusters.…”

Section: Introductionmentioning

confidence: 99%

Insight into the Geometric and Electronic Structures of Gold/Silver Superatomic Clusters Based on Icosahedron M₁₃ Units and Their Alloys

Jin

Wang

Zhu

2019

Chemistry An Asian Journal

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Metal superatomic nanoclusters, with electronic structures similar to those of one certain atom, are an important type of metal clusters. Interestingly, metal clusters with metal cores composed of either icosahedral M13 or icosahedral assemblies always have a greater potential to become superatomic clusters. Furthermore, superatomic clusters with similar electronic compositions could possess various geometric structures, owing to differences in the shells; this provides a deeper understanding of the metal superatomic cluster and the assembly for nanomaterials. Therefore, this review focuses on the geometric and electronic structures of gold/silver superatomic clusters based on icosahedron M13 units and their alloys, which will facilitate the development of various applications of superatomic clusters.

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“…Great progress has been achieved in the structure determination of metal nanoclusters. To date, a series of metal nanoclusters have been revealed, especially Au nanoclusters, Au 16 , Au 18 , Au 21 , Au 23 , Au 24 , Au 25 , Au 28 , Au 30 , Au 36 , Au 38 , Au 60 , Au 92 , Au 102 , Au 130 , Au 133 , Au 144 , Au 246 , and Au 279 . In contrast, there are only a relatively limited number of thiolated silver nanoclusters with well‐defined crystal structure, including Ag 25 , Ag 29 , Ag 44 , Ag 141 , Ag 136 , and Ag 374 .…”

Section: Methodsmentioning

confidence: 99%

Cu²⁺‐Induced Structural Isomers: Effect of Foreign Metal Ions on the Structure and Properties of Silver Nanoclusters

Lin

Liu

et al. 2019

Chemistry An Asian Journal

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Metal ions have an important impact on the precise control of the synthesis and atomic structural arrangement of noble metal nanoclusters. In this work, the effect of metal ions on the isomer generation of metal nanoclusters is revealed for the first time. Compared with the previous Ag23 nanoclusters with two face‐centered cubic (fcc) unit cells twisting 27°, the Ag23 isomer had a higher symmetry structure with two fcc unit cells almost overlapping. In addition, the UV/Vis absorption spectrum of the isomer showed a slight redshift of approximately 14 nm. The redshift might be because of the modulation of electronic structure, which is derived from fine‐tuned crystal structure. Based on the experimental results, we provide mechanisms to explain the Cu2+ effect on the structural isomer. This work reports a significant finding to tune precisely the crystal structure and understand the mechanism of shape‐controlled synthesis of metal nanoclusters.

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Total Structure Determination of Au₁₆(S-Adm)₁₂ and Cd₁Au₁₄(StBu)₁₂ and Implications for the Structure of Au₁₅(SR)₁₃

Cited by 83 publications

References 55 publications

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Insight into the Geometric and Electronic Structures of Gold/Silver Superatomic Clusters Based on Icosahedron M₁₃ Units and Their Alloys

Cu²⁺‐Induced Structural Isomers: Effect of Foreign Metal Ions on the Structure and Properties of Silver Nanoclusters

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Total Structure Determination of Au16(S-Adm)12 and Cd1Au14(StBu)12 and Implications for the Structure of Au15(SR)13

Cited by 83 publications

References 55 publications

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Insight into the Geometric and Electronic Structures of Gold/Silver Superatomic Clusters Based on Icosahedron M13 Units and Their Alloys

Cu2+‐Induced Structural Isomers: Effect of Foreign Metal Ions on the Structure and Properties of Silver Nanoclusters

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Product

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Total Structure Determination of Au₁₆(S-Adm)₁₂ and Cd₁Au₁₄(StBu)₁₂ and Implications for the Structure of Au₁₅(SR)₁₃

Insight into the Geometric and Electronic Structures of Gold/Silver Superatomic Clusters Based on Icosahedron M₁₃ Units and Their Alloys

Cu²⁺‐Induced Structural Isomers: Effect of Foreign Metal Ions on the Structure and Properties of Silver Nanoclusters