Fcc versus Non‐fcc Structural Isomerism of Gold Nanoparticles with Kernel Atom Packing Dependent Photoluminescence

Zhuang, Shengli; Liao, Lingwen; Yuan, Jie; Xia, Nan; Zhao, Yan; Wang, Chengming; Gan, Zibao; Yan, Nan; He, Lizhong; Li, Jin; Deng, Haiteng; Guan, Zhaoyong; Yang, Jinlong; Wu, Zhikun

doi:10.1002/ange.201813426

Cited by 12 publications

(11 citation statements)

References 65 publications

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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%

“…[179] The kernel of Au 42 (TBBT) 26 -F 180 is the same as that in Au 44 (TBBT) 28 of high HCM value, and Au 42 (TBBT) 26 -N shows a "twist mirror symmetry." [181] Au 43 (S-c-C 6 H 11 ) 25 , [182] Au 48 (TBBT) 28 , [183] Au 49 (2,4-DMBT) 27 , [184] Au 146 (p-MBA) 57 , [185] and Au 279 (TBBT) 84 [186,187] are all lack of symmetry, thus, all chiral. There are two Au 36 nanoclusters reported.…”

Section: Achiral/chiral Au-sr Ncsmentioning

confidence: 99%

“…Au 42 (S‐ c ‐C 6 H 11 ) 26 adopts quasi‐ D 2 symmetry based on its double‐helical kernel and the arrangement of staple motifs 179. The kernel of Au 42 (TBBT) 26 ‐F 180 is the same as that in Au 44 (TBBT) 28 of high HCM value, and Au 42 (TBBT) 26 ‐N shows a “twist mirror symmetry.”181 Au 43 (S‐ c ‐C 6 H 11 ) 25 ,182 Au 48 (TBBT) 28 ,183 Au 49 (2,4‐DMBT) 27 ,184 Au 146 ( p ‐MBA) 57 ,185 and Au 279 (TBBT) 84 186,187 are all lack of symmetry, thus, all chiral.…”

Section: Summary Of the Au Ncs With Different Types Of Ligandsmentioning

confidence: 99%

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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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Section: Achiral/chiral Au-sr Ncsmentioning

confidence: 99%

Section: Achiral/chiral Au-sr Ncsmentioning

confidence: 99%

Section: Summary Of the Au Ncs With Different Types Of Ligandsmentioning

confidence: 99%

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Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

et al. 2020

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“…Despite recent advances in controllable synthesis and structure determination of atomically precise nanoclusters 9 – 18 , the concept of reversible conformational isomerization for metal nanoclusters has not yet been explored. To date, irreversible structural isomerization of atomically precise nanoclusters has been reported in a few cases 19 – 24 . One case pertains to Au 42 (TBBT) 26 (TBBT = 4-tert-butylbenzenethiolate) in the form of fcc and non-fcc frameworks that were synthesized via two different procedures 19 .…”

Section: Introductionmentioning

confidence: 99%

“…To date, irreversible structural isomerization of atomically precise nanoclusters has been reported in a few cases 19 – 24 . One case pertains to Au 42 (TBBT) 26 (TBBT = 4-tert-butylbenzenethiolate) in the form of fcc and non-fcc frameworks that were synthesized via two different procedures 19 . However, the two isomeric structures of Au 42 are “static” and cannot be reversibly transformed 19 .…”

Section: Introductionmentioning

confidence: 99%

Atomically precise nanoclusters with reversible isomeric transformation for rotary nanomotors

et al. 2020

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Thermal-stimuli responsive nanomaterials hold great promise in designing multifunctional intelligent devices for a wide range of applications. In this work, a reversible isomeric transformation in an atomically precise nanocluster is reported. We show that biicosahedral [Au13Ag12(PPh3)10Cl8]SbF6 nanoclusters composed of two icosahedral Au7Ag6 units by sharing one common Au vertex can produce two temperature-responsive conformational isomers with complete reversibility, which forms the basis of a rotary nanomotor driven by temperature. Differential scanning calorimetry analysis on the reversible isomeric transformation demonstrates that the Gibbs free energy is the driving force for the transformation. This work offers a strategy for rational design and development of atomically precise nanomaterials via ligand tailoring and alloy engineering for a reversible stimuli-response behavior required for intelligent devices. The two temperature-driven, mutually convertible isomers of the nanoclusters open up an avenue to employ ultra-small nanoclusters (1 nm) for the design of thermal sensors and intelligent catalysts.

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Traceless Removal of Two Kernel Atoms in a Gold Nanocluster and Its Impact on Photoluminescence

et al. 2021

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Removing or adding kernel atoms of metal nanoclusters (NCs) without leaving a trace is a substantial challenge because the kernel atoms are inside and covered by the outer staples. However, such kernel tuning is very important for improving the properties and acquiring an in‐depth understanding of the kernel‐property correlation. Photoluminescence (PL) is one of the most intriguing characteristics of metal NCs but has not been well understood until now. Inspired by these challenges/questions, we conducted this study and, for the first time, achieved the traceless removal of two kernel atoms in a gold nanocluster by applying a simple thermal treatment and revealed its impact on PL. Further, we demonstrated that the kernel Au‐Au bond length can be an indicator for a comparison of the PL or kernel charge state between nanoclusters with similar kernel structures and sizes.

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Fcc versus Non‐fcc Structural Isomerism of Gold Nanoparticles with Kernel Atom Packing Dependent Photoluminescence

Cited by 12 publications

References 65 publications

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Atomically precise nanoclusters with reversible isomeric transformation for rotary nanomotors

Traceless Removal of Two Kernel Atoms in a Gold Nanocluster and Its Impact on Photoluminescence

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