A Chiral Luminescent Au<sub>16</sub>Ring Self-Assembled from Achiral Components

Yu, Shu‐Yan; Zhang, Zhongxing; Cheng, Eddie Chung‐Chin; Li, Yi‐Zhi; Yam, Vivian Wing‐Wah; Huang, Haiping; Zhang, Rongben

doi:10.1021/ja0565727

Cited by 132 publications

(89 citation statements)

References 27 publications

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“…The peak at 370 nm in the absorption spectrum of type-I complexes was associated with the metallophilic interaction between the metal centers (Ag I Á Á Á Ag I ), which is well-documented for closed-shell metal atoms (Ag I has 4d 10 center). [60][61][62] The formation of metallophilic bonds between the thiolate-Ag I complexes implied that there was a certain extent of intermolecular aggregations in the type-I complexes, as confirmed by its ESI mass spectrum. As shown in Figure 1b (top panel), the species in the type-I thiolate-Ag I complexes displayed a very broad size range from Ag 1 to Ag 11 (or Ag 1-11 species, see Supplementary Figure S1 for their detailed isotope patterns).…”

Section: Resultsmentioning

confidence: 82%

Highly luminescent silver nanoclusters with tunable emissions: cyclic reduction–decomposition synthesis and antimicrobial properties

et al. 2013

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This paper reports a facile aqueous-based synthesis method for highly luminescent Ag nanoclusters (NCs) with tunable emissions. The key strategy was to use a reduction-decomposition-reduction cycle to modify the Ag NC intermediates that were further subjected to size/structure focusing. The as-modified Ag NC intermediates were more robust in water against the subsequent etching by thiol ligands, making a mild size-/structure-focusing environment possible, which produced highly luminescent Ag NCs with a well-defined size and structure. Ag NCs with intense red and green emission were successfully synthesized by this method. These Ag NCs possessed a well-defined size and structure (Ag 16 (SG) 9 and Ag 9 (SG) 6 ), and exhibited excellent stability in the aqueous phase. Our highly luminescent Ag NCs also possessed superior antimicrobial properties against the multidrug-resistant bacteria Pseudomonas aeruginosa, via generating a high concentration of intracellular reactive oxygen species. Keywords: antimicrobial; biomedical applications; luminescence; silver nanoclusters; thiol ligands INTRODUCTION Ultrasmall noble metal nanoclusters (NCs), typically composed of several to a hundred metal atoms, present unique physical and chemical properties between single atoms and large nanocrystals (42 nm). [1][2][3][4] Owing to the strong quantum size confinement in this size range (o 2 nm), NCs possess discrete and size-tunable electronic transitions and display unique molecule-like properties, such as quantized charging and luminescence. [5][6][7][8][9][10][11][12] Strong luminescence is one of the most attractive features of these NCs owing to their ultrafine size, good photostability and low toxicity; 13 some of these properties may not be realized by other luminophores, such as organic dyes (for example, photostability concerns) and semiconductor quantum dots (for example, relatively large size and toxicity concerns). 2,8,9,14,15 Recent studies have shown that luminescent Au and Ag NCs are promising optical probes for bioimaging and biosensing applications. 4,[16][17][18][19][20] This finding has led to the development of various methods for the synthesis of highly luminescent Au and Ag NCs. 2,21 On the other hand, insofar as nanostructured Ag-based materials are concerned, they are finding an increasing usage for antimicrobial applications owing to the unique chemistry of Ag interfacing with microorganisms. [22][23][24] Although there is a large volume of work exploring the potential use of large Ag

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Section: Resultsmentioning

confidence: 82%

Highly luminescent silver nanoclusters with tunable emissions: cyclic reduction–decomposition synthesis and antimicrobial properties

et al. 2013

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“…[24][25][26][27][28] In the ring structures, Au I atoms are exclusively bridged by thiolates (SR), and there is aurophilic interaction between Au I atoms. Experimentally, a Au I 16 thiolate ring [29] shows an average Au I ···Au I separation of 3.12 , which is much shorter than the sum of van der Waals radii of gold (2r vdW = 3.32 ), hence, indicating Au I ···Au I interaction. Another example is the Au I 12 L 6 (L = anion of the bicarbodithiolate ligand) ring.…”

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confidence: 96%

Quantum‐Sized Gold Nanoclusters: Bridging the Gap between Organometallics and Nanocrystals

Jin

Zhu

2011

Chemistry A European J

145

116

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This Concept article provides an elementary discussion of a special class of large-sized gold compounds, so-called Au nanoclusters, which lies in between traditional organogold compounds (e.g., few-atom complexes, <1 nm) and face-centered cubic (fcc) crystalline Au nanoparticles (typically >2 nm). The discussion is focused on the relationship between them, including the evolution from the Au⋅⋅⋅Au aurophilic interaction in Au(I) complexes to the direct Au-Au bond in clusters, and the structural transformation from the fcc structure in nanocrystals to non-fcc structures in nanoclusters. Thiolate-protected Au(n)(SR)(m) nanoclusters are used as a paradigm system. Research on such nanoclusters has achieved considerable advances in recent years and is expected to flourish in the near future, which will bring about exciting progress in both fundamental scientific research and technological applications of nanoclusters of gold and other metals.

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“…Among the gold(I) complexes, polynuclear gold(I) chalcogenido complexes represent an important and interesting class (44)(45)(46)(47)(48)(49)(50)(51). While directed supramolecular assembly of discrete Au 12 (52), Au 16 (53), Au 18 (51), and Au 36 (54) metallomacrocycles as well as trinuclear gold (I) columnar stacks (34)(35)(36)(37)(38) have been reported, there have been no corresponding studies on the supramolecular hierarchical assembly of polynuclear gold(I) chalcogenido clusters.…”

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Luminescence color switching of supramolecular assemblies of discrete molecular decanuclear gold(I) sulfido complexes

Hau

Lee

Cheng

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

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A series of discrete decanuclear gold(I) μ 3 -sulfido complexes with alkyl chains of various lengths on the aminodiphosphine ligands, [Au 10 {Ph 2 PN(C n H 2n+1 )PPh 2 } 4 (μ 3 -S) 4 ](ClO 4 ) 2 , has been synthesized and characterized. These complexes have been shown to form supramolecular nanoaggregate assemblies upon solvent modulation. The photoluminescence (PL) colors of the nanoaggregates can be switched from green to yellow to red by varying the solvent systems from which they are formed. The PL color variation was investigated and correlated with the nanostructured morphological transformation from the spherical shape to the cube as observed by transmission electron microscopy and scanning electron microscopy. Such variations in PL colors have not been observed in their analogous complexes with short alkyl chains, suggesting that the long alkyl chains would play a key role in governing the supramolecular nanoaggregate assembly and the emission properties of the decanuclear gold(I) sulfido complexes. The long hydrophobic alkyl chains are believed to induce the formation of supramolecular nanoaggregate assemblies with different morphologies and packing densities under different solvent systems, leading to a change in the extent of Au(I)-Au(I) interactions, rigidity, and emission properties.luminescence | color switching | nanoaggregate | gold cluster G old(I) complexes are one of the fascinating classes of complexes that reveal photophysical properties that are highly sensitive to the nuclearity of the metal centers and the metalmetal distances (1-59). In a certain sense, they bear an analogy or resemblance to the interesting classes of metal nanoparticles (NPs) (60-69) and quantum dots (QDs) (70)(71)(72)(73)(74)(75)(76) in that the properties of the nanostructured materials also show a strong dependence on their sizes and shapes. Interestingly, while the optical and spectroscopic properties of metal NPs and QDs show a strong dependence on the interparticle distances, those of polynuclear gold(I) complexes are known to mainly depend on the nuclearity and the internuclear separations of gold(I) centers within the individual molecular complexes or clusters, with influence of the intermolecular interactions between discrete polynuclear molecular complexes relatively less explored (34-38), and those of polynuclear gold(I) clusters not reported. Moreover, while studies on polynuclear gold(I) complexes or clusters are known (34-54), less is explored of their hierarchical assembly and nanostructures as well as the influence of intercluster aggregation on the optical properties (34-38). Among the gold(I) complexes, polynuclear gold(I) chalcogenido complexes represent an important and interesting class (44-51). While directed supramolecular assembly of discrete Au 12 (52), Au 16 (53), Au 18 (51), and Au 36 (54) metallomacrocycles as well as trinuclear gold (I) columnar stacks (34-38) have been reported, there have been no corresponding studies on the supramolecular hierarchical assembly of polynuclear gold(I) chalc...

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A Chiral Luminescent Au₁₆Ring Self-Assembled from Achiral Components

Abstract: A luminescent supramolecular chiral Au16 ring with 4.822 nm perimeter that self-assembled from a tetrameric array of achiral Au2 units is described. Intra- and intermolecular Au...Au interactions play an important role in directing its chiral self-assembly.

Cited by 132 publications

References 27 publications

Highly luminescent silver nanoclusters with tunable emissions: cyclic reduction–decomposition synthesis and antimicrobial properties

Highly luminescent silver nanoclusters with tunable emissions: cyclic reduction–decomposition synthesis and antimicrobial properties

Quantum‐Sized Gold Nanoclusters: Bridging the Gap between Organometallics and Nanocrystals

Luminescence color switching of supramolecular assemblies of discrete molecular decanuclear gold(I) sulfido complexes

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A Chiral Luminescent Au16Ring Self-Assembled from Achiral Components

Abstract: A luminescent supramolecular chiral Au16 ring with 4.822 nm perimeter that self-assembled from a tetrameric array of achiral Au2 units is described. Intra- and intermolecular Au...Au interactions play an important role in directing its chiral self-assembly.

Cited by 132 publications

References 27 publications

Highly luminescent silver nanoclusters with tunable emissions: cyclic reduction–decomposition synthesis and antimicrobial properties

Highly luminescent silver nanoclusters with tunable emissions: cyclic reduction–decomposition synthesis and antimicrobial properties

Quantum‐Sized Gold Nanoclusters: Bridging the Gap between Organometallics and Nanocrystals

Luminescence color switching of supramolecular assemblies of discrete molecular decanuclear gold(I) sulfido complexes

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A Chiral Luminescent Au₁₆Ring Self-Assembled from Achiral Components