Synthesis and Characterization of Three Multi‐Shell Metalloid Gold Clusters Au32(R3P)12Cl8

Kenzler, Sebastian; Fetzer, Florian; Schrenk, Claudio; Pollard, Nia; Frojd, Andrew R.; Clayborne, Andre; Schnepf, Andreas

doi:10.1002/anie.201900644

Cited by 50 publications

(72 citation statements)

References 44 publications

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“…Further, we observe an aspect ratio of the long and short axis of A/B = 1.64 and a sharp edge angle of Δ = 63° for all microcrystals. This aspect ratio corresponds to the associated ratio found in the unit cell of macroscopic Au 32 -NC crystals, and the angle Δ suits the γ -angle of the unit cell of γ = 63.4° 32 . Hence, the shape of the microcrystals strongly resembles the aforementioned unit cell which renders the crystals idiomorphic.…”

Section: Resultsmentioning

confidence: 99%

“…The atomically precise building blocks of metalloid Au 32 ( n Bu 3 P) 12 Cl 8 nanoclusters (abbreviated as Au 32 -NCs) with an Au-core size of ~0.9 nm are synthesized as previously described 32 . Including the full ligand shell of twelve phosphine ligands and eight chlorine atoms, the building block size is about 1.3 nm, displayed in Fig.…”

Section: Resultsmentioning

confidence: 99%

“…1a . Single-crystal X-ray diffraction of macroscopic crystals of Au 32 -NCs yields a triclinic unit cell containing two crystallographically independent NCs ( a = 1.91 nm, b = 1.93 nm, c = 3.32 nm; α = 73.2°, ß = 86.7°, γ = 63.4°, space group P ) 32 .

Fig.…”

Section: Resultsmentioning

confidence: 99%

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Structural order enhances charge carrier transport in self-assembled Au-nanoclusters

et al. 2020

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The collective properties of self-assembled nanoparticles with long-range order bear immense potential for customized electronic materials by design. However, to mitigate the shortcoming of the finite-size distribution of nanoparticles and thus, the inherent energetic disorder within assemblies, atomically precise nanoclusters are the most promising building blocks. We report an easy and broadly applicable method for the controlled self-assembly of atomically precise Au32(nBu3P)12Cl8 nanoclusters into micro-crystals. This enables the determination of emergent optoelectronic properties which resulted from long-range order in such assemblies. Compared to the same nanoclusters in glassy, polycrystalline ensembles, we find a 100-fold increase in the electric conductivity and charge carrier mobility as well as additional optical transitions. We show that these effects are due to a vanishing energetic disorder and a drastically reduced activation energy to charge transport in the highly ordered assemblies. This first correlation of structure and electronic properties by comparing glassy and crystalline self-assembled superstructures of atomically precise gold nanoclusters paves the way towards functional materials with novel collective optoelectronic properties.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Structural order enhances charge carrier transport in self-assembled Au-nanoclusters

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“…Chiral Au-phosphine NCs: [Au 7 ( DPPP) 4 ] 3+ , [193] [Au 8 (DPPP) 4 ] 2+ , [194] [Au 11 (DPPE) 6 ] 3+ , [195] [Au 11 (PPh 3 ) 8-Cl 2 ] + , [196] [Au 13 (DPPE) 5 Cl 2 ] 3+ , [197] [Au 19 (Akn) 9 (DPPA) 3 ] 2+ , [149] [Au 2 0 (PP 3 ) 4 ] 4+ , [198] [Au 23 (Akn) 9 (PPh 3 )] 2+ , [199] [Au 38 (SR) 20 (PPh 3 ) 4 ] 2+ , [153] [Au 39 (PPh 3 ) 14 Cl 6 ] 2+ , [200] [Au 40 (Akn) 20 (DPPM) 4 ] 4+ . [201] Achiral Au-phosphine NCs: Au 6 (DPPP) 4 ] 2+ , [202] [Au 8 (Akn) 2 (DPPP) 4 ] 2+ , [203] [Au 9 (PPh 3 ) 8 ] 3+ , [204] [Au 11 (P Ph 3 ) 7 Cl 3 ] + , [196,205] [Au 13 (PR 3 ) 10 Cl 2 ] 3+ , [206] [Au 18 (DPPM) 6 Cl 4 ] 4+ , [207] [Au 20 (PPhpy 2 ) 10 Cl 4 ] 2+ , [208] [Au 24 (Akn) 14 (PPh 3 ) 4 ] 2+ , [171] [Au 24 (SR) 5 (PPh 3 ) 10 Cl 2 ] + , [170] [Au 25 (SR) 5 (PPh 3 ) 10 Cl 2 ] 2+ , [154] Au 32 (PR 3 ) 12 Cl 8 , [209] [Au 37 (SR) 10 (PPh 3 ) 10 Cl 2 ] + , [210] [Au 60 Se 2 (SeR) 15 (PPh 3 ) 10 ] + , [211] Au 108 S 24 (PPh 3 ) 16 . [212] From Scheme 4 we can see that for Au NCs without or with few staple motifs, the number of achiral structures is more than that of chiral ones, while for those with surface staple motifs as shown in Scheme 3, the chiral ones obviously outnumber their achiral counterparts.…”

Section: From Top Left To Bottom Rightmentioning

confidence: 99%

“…Achiral Au–phosphine NCs: Au 6 (DPPP) 4 ] 2+ ,202 [Au 8 (Akn) 2 (DPPP) 4 ] 2+ ,203 [Au 9 (PPh 3 ) 8 ] 3+ ,204 [Au 11 (PPh 3 ) 7 Cl 3 ] + ,196,205 [Au 13 (PR 3 ) 10 Cl 2 ] 3+ ,206 [Au 18 (DPPM) 6 Cl 4 ] 4+ ,207 [Au 20 (PPhpy 2 ) 10 Cl 4 ] 2+ ,208 [Au 24 (Akn) 14 (PPh 3 ) 4 ] 2+ ,171 [Au 24 (SR) 5 (PPh 3 ) 10 Cl 2 ] + ,170 [Au 25 (SR) 5 (PPh 3 ) 10 Cl 2 ] 2+ ,154 Au 32 (PR 3 ) 12 Cl 8 ,209 [Au 37 (SR) 10 (PPh 3 ) 10 Cl 2 ] + ,210 [Au 60 Se 2 (SeR) 15 (PPh 3 ) 10 ] + ,211 Au 108 S 24 (PPh 3 ) 16 212…”

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

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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Gold Nanoclusters as Nanoantibiotic Auranofin Analogues

Ndugire

Raviranga

Lao

et al. 2021

Adv Healthcare Materials

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Auranofin, a gold(I)‐complex with tetraacetylated thioglucose (Ac4GlcSH) and triethylphosphine ligands, is an FDA‐approved drug used as an anti‐inflammatory aid in the treatment of rheumatoid arthritis. In repurposing auranofin for other diseases, it was found that the drug showed significant activity against Gram‐positive but was inactive against Gram‐negative bacteria. Herein, the design and synthesis of gold nanoclusters (AuNCs) based on the structural motif of auranofin are reported. Phosphine‐capped AuNCs are synthesized and glycosylated, yielding auranofin analogues with mixed triphenylphosphine monosulfonate (TPPMS)/Ac4GlcSH ligand shells. These AuNCs are active against both Gram‐negative and Gram‐positive bacteria, including multidrug‐resistant pathogens. Notably, an auranofin analogue, a mixed‐ligand 1.6 nm AuNC 4b, is more active than auranofin against Pseudomonas aeruginosa, while exhibiting lower toxicity against human A549 cells. The enhanced antibacterial activity of these AuNCs is characterized by a greater uptake of Au by the bacteria compared to AuI complexes. Additional factors include increased oxidative stress, moderate inhibition of thioredoxin reductase (TrxR), and DNA damage. Most intriguingly, the uptake of AuNCs are not affected by the bacterial outer membrane (OM) barrier or by binding with the extracellular proteins. This contrasts with AuI complexes like auranofin that are susceptible to protein binding and hindered by the OM barrier.

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Synthesis and Characterization of Three Multi‐Shell Metalloid Gold Clusters Au₃₂(R₃P)₁₂Cl₈

Cited by 50 publications

References 44 publications

Structural order enhances charge carrier transport in self-assembled Au-nanoclusters

Structural order enhances charge carrier transport in self-assembled Au-nanoclusters

Chirality and Surface Bonding Correlation in Atomically Precise Metal Nanoclusters

Gold Nanoclusters as Nanoantibiotic Auranofin Analogues

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