Chiroptical Activity Enhancement via Structural Control: The Chiral Synthesis and Reversible Interconversion of Two Intrinsically Chiral Gold Nanoclusters

Wang, Jiaqi; Guan, Zong‐Jie; Liu, Wendi; Yang, Yang; Wang, Quan‐Ming

doi:10.1021/jacs.8b11096

Cited by 111 publications

(91 citation statements)

References 51 publications

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“…To this end, the overall transformation from Au 6 to Au 8 Cl 2 was found to be determined exclusively by the easiness of the Au−P bond dissociation, which originates from the core charge density. Of note, the Au−P bond dissociation was also reported in some other electron‐rich metal cluster systems …”

Section: Resultssupporting

confidence: 58%

Core Charge Density Dominated Size‐Conversion from Au₆P₈ to Au₈P₈Cl₂

Zhao

Weng

et al. 2020

Chemistry A European J

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The stimulus-response of metal nanoclusters is crucial to their applications in catalysis and bio-clinics, etc. However,i ts mechanistic origin has not been well studied. Herein, the mechanism of the Au I PPh 3 Cl-induced size-conversion from [Au 6 (DPPP) 4 ] 2 + to [Au 8 (DPPP) 4 Cl 2 ] 2 + (DPPP is short for 1,3-bis(diphenylphosphino)propane) is theoretically investigated with density functional theory (DFT) calculations. The optimal size-growth pathway,a nd the key structural parameters were elucidated. The AuÀPb ond dissociation steps are key to the size-growth, the easinesso fw hich was determined by the charged ensity of the metallic core of the clusterp recursors (i.e.," core charge density"). This study sheds light on the inherents tructure-reactivity relationships during the size-conversion, and will benefitt he deep understanding on the kinetics of more complex systems. Scheme1.Atomic structure of [Au 6 (DPPP) 4 ] 2 + and [Au 8 (DPPP) 4 Cl 2 ] 2 + cited from single-crystal X-ray diffraction. [18] For clarity,the phenyl groupo nt he DPPPl igands and all hydrogen atoms wereo mitted.

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Section: Resultssupporting

confidence: 58%

Core Charge Density Dominated Size‐Conversion from Au₆P₈ to Au₈P₈Cl₂

Zhao

Weng

et al. 2020

Chemistry A European J

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“…These results suggested that different chirality were induced in 1 by the enantiomers. 58,59 More importantly, 1 ⊃ D-MT and 1 ⊃ L-MT exhibited CPL responses in the wavelength region of 400-550 nm (Figure 3b). The measured luminescence anisotropy factor (g lum factor) at 467 nm was 1.5 × 10 −3 , thereby, demonstrating that the CPL emission was realized in 1 by encapsulating chiral guest molecules.…”

Section: Resultsmentioning

confidence: 96%

Mesoporous Crystalline Silver-Chalcogenolate Cluster-Assembled Material with Tailored Photoluminescence Properties

Wang

Yan

et al. 2019

CCS Chem

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Crystalline cluster-assembled materials (CAMs) are emerging as types of exploratory fabrications due to their atomically precise structures and intriguing chemical/physical properties, as well as their luminescent function. However, constructing novel luminescent porous crystalline CAMs present an enduring and significant challenge owing to their instability and poor ambient-temperature photoluminescent quantum yields. In this work, we synthesized successfully, a mesoporous crystalline CAM (1 ⊃ DMAC), based on silver-chalcogenolate cluster and 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (TPPE) ligand, with highsymmetry structure and ultralarge pores. 1 ⊃ DMAC exhibited adjustable intense luminescence, originating from aggregation-induced emission (AIE) properties of the TPPE ligand. The diameter of the cubic cage in 1 ⊃ DMAC was as high as 32 Å, which endowed it with satisfactory encapsulation capacity for different guest molecules. Interestingly, by adjusting functionalized guest molecules, circularly polarized luminescence, white-light-emitting, and room-temperature phosphorescence were readily realized. 1 ⊃ DMAC could enrich limited kinds of mesoporous crystalline CAMs and offers the prospect of application in host-guest chemistry. More importantly, this work provides a strategy, versatile for tailoring luminescence in crystalline porous materials.

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“…It is interesting to mention that enantiopure [Au 9 ( R ‐/ S ‐BINAS) 4 ] 3+ (Au 9 ) and Au 10 ( R ‐/ S ‐BINAS) 4 (Akn)] 3+ (Au 10 , Akn = p ‐CF 3 C 6 H 4 CC) nanoclusters obtained by enantioselective synthesis can be reversibly interconverted into each other by addition or removal of p ‐CF 3 C 6 H 4 CCAu. Both clusters show large anisotropy factors, and the chiroptical activity can be modulated by structural control ( Figure ) 283. More information about chiroptical molecules based on binaphthyl derivatives can be found in previous review 2…”

Section: Methods For Obtaining Chiroptically Active Metal Nanoclustersmentioning

confidence: 96%

“…Both clusters show large anisotropy factors, and the chiroptical activity can be modulated by structural control (Figure 18). [283] More information about chiroptical molecules based on binaphthyl derivatives can be found in previous review. [2] Modified BINAP, i.e., (R)-or (S)-2,2′-bis(di-p-tolylphosphino)-1,1′-binaphthyl (Tol-BINAP) could achieve in enantiopure…”

Section: Enantioselective Synthesismentioning

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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Chiroptical Activity Enhancement via Structural Control: The Chiral Synthesis and Reversible Interconversion of Two Intrinsically Chiral Gold Nanoclusters

Cited by 111 publications

References 51 publications

Core Charge Density Dominated Size‐Conversion from Au₆P₈ to Au₈P₈Cl₂

Core Charge Density Dominated Size‐Conversion from Au₆P₈ to Au₈P₈Cl₂

Mesoporous Crystalline Silver-Chalcogenolate Cluster-Assembled Material with Tailored Photoluminescence Properties

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

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Chiroptical Activity Enhancement via Structural Control: The Chiral Synthesis and Reversible Interconversion of Two Intrinsically Chiral Gold Nanoclusters

Cited by 111 publications

References 51 publications

Core Charge Density Dominated Size‐Conversion from Au6P8 to Au8P8Cl2

Core Charge Density Dominated Size‐Conversion from Au6P8 to Au8P8Cl2

Mesoporous Crystalline Silver-Chalcogenolate Cluster-Assembled Material with Tailored Photoluminescence Properties

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

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Core Charge Density Dominated Size‐Conversion from Au₆P₈ to Au₈P₈Cl₂

Core Charge Density Dominated Size‐Conversion from Au₆P₈ to Au₈P₈Cl₂