Isolation and Total Structure Determination of an All‐Alkynyl‐Protected Gold Nanocluster Au<sub>144</sub>

Lei, Zhijun; Li, Jiao‐Jiao; Wan, Xian‐Kai; Zhang, Wen‐Han; Wang, Quan‐Ming

doi:10.1002/ange.201804481

Cited by 46 publications

(15 citation statements)

References 75 publications

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“…The popular Perdew−Burke−Ernzerhof (PBE) GGA functional has been the de facto choice for structural and energetic studies of atomically precise nanoclusters, due to a well-demonstrated balance of accuracy and computational cost. 6 DFT-PBE's famous successes include structure prediction for Au 25 (SR) 18 and Au 38 (SR) 24 that were confirmed by experiment. 6,7 In terms of the interaction between electrons and the nuclei, the effective core potentials or pseudopotentials including the scalar relativistic effects are routinely employed for cluster systems with heavy metals such as Au.…”

Section: Density Functional Theory In Cluster Researchmentioning

confidence: 91%

Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles

et al. 2018

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Conspectus Atomically precise, ligand-protected metal nanoclusters are of great interest for their well-defined structures, intriguing physicochemical properties, and potential applications in catalysis, biology, and nanotechnology. Their structure precision provides many opportunities to correlate their geometries, stability, electronic properties, and catalytic activities by closely integrating theory and experiment. In this Account, we highlight recent theoretical advances from our efforts to understand the metal–ligand interfaces, the energy landscape, the electronic structure and optical absorption, and the catalytic applications of atomically precise metal nanoclusters. We mainly focus on gold nanoclusters. The bonding motifs and energetics at the gold–ligand interfaces are two main interests from a computational perspective. For the gold–thiolate interface, the −RS–Au–SR– staple motif is not always preferred; in fact, the bridging motif (−SR−) is preferred at the more open facets such as Au(100) and Au(110). This finding helps understand the diversity of the gold–thiolate motifs for different core geometries and sizes. A great similarity is demonstrated between gold–thiolate and gold–alkynyl interfaces, regarding formation of the staple-type motifs with PhCC– as an example. In addition, N-heterocyclic carbenes (NHCs) without bulky groups also form the staple-type motif. Alkynyls and bulky NHCs have the strongest binding with the gold surface from comparing 27 ligands of six types, suggesting a potential to synthesize NHC-protected gold clusters. The energy landscape of nanosystems is usually complex, but experimental progress in synthesizing clusters of the same Au–S composition with different R groups and isomers of the same Au n (SR) m formula have made detailed theoretical analyses of energetic contributions possible. Ligand–ligand interactions turn out to play an important role in the cluster stability, while metastable isomers can be obtained via kinetic control. Although the superatom-complex theory is the starting point to understand the electronic structure of atomically precise gold clusters, other factors also greatly affect the orbital levels that manifest themselves in the experimental optical absorption spectra. For example, spin–orbit coupling needs to be included to reproduce the splitting of the HOMO–LUMO transition observed experimentally for Au25(SR)18 –, the poster child of the family. In addition, doping can lead to structural changes and charge states that do not follow the superatomic electron count. Atomically precise metal nanoclusters are an ideal system for understanding nanocatalysis due to their well-defined structures. Active sites and catalytic mechanisms are explored for selective hydrogenation and hydrogen evolution on thiolate-protected gold nanoclusters with and without dopants. The behavior of H in nanogold is analyzed in detail, and the most promising site to attract H is found to be coordinately unsaturated Au atoms. Many insights have been gained from first-principle...

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Section: Density Functional Theory In Cluster Researchmentioning

confidence: 91%

Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles

et al. 2018

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“…28 In this case, the gold precursor is reduced by sodium borohydride in the presence of thiolcontaining ligands. Depending on the synthesis parameters, the formed gold nanoparticles have a size of ∼2 nm, 28 i.e., close to the size of atom-sharp gold clusters like Au 102 (pMBA) 44 (pMBA = p-mercaptobenzoic acid), 29 Au 70 S 20 (PPh 3 ) 12 , 30 Au 144 (CCAr) 60 , 31 (AuAg) 267 (SR) 80 , 32 and (AuAg) 45 -(SR) 27 (PPh 3 ) 6 . 32 Copper-catalyzed azide−alkyne cycloaddition (CuAAC) has emerged as a popular bioconjugation tool in the past decade.…”

Section: ■ Introductionmentioning

confidence: 99%

Click Chemistry on the Surface of Ultrasmall Gold Nanoparticles (2 nm) for Covalent Ligand Attachment Followed by NMR Spectroscopy

et al. 2019

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Ultrasmall gold nanoparticles (core diameter 2 nm) were surface-conjugated with azide groups by attaching the azide-functionalized tripeptide lysine(N3)-cysteine-asparagine with ∼117 molecules on each nanoparticle. A covalent surface modification with alkyne-containing molecules was then possible by copper-catalyzed click chemistry. The successful clicking to the nanoparticle surface was demonstrated with 13C-labeled propargyl alcohol. All steps of the nanoparticle surface conjugation were verified by extensive NMR spectroscopy on dispersed nanoparticles. The particle diameter and the dispersion state were assessed by high-resolution transmission electron microscopy (HRTEM), differential centrifugal sedimentation (DCS), and 1H-DOSY NMR spectroscopy. The clicking of fluorescein (FAM-alkyne) gave strongly fluorescing ultrasmall nanoparticles that were traced inside eukaryotic cells. The uptake of these nanoparticles after 24 h by HeLa cells was very efficient and showed that the nanoparticles even penetrated the nuclear membrane to a very high degree (in contrast to dissolved FAM-alkyne alone that did not enter the cell). About 8 fluorescein molecules were clicked to each nanoparticle.

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“…20 Wang et al have recently reported the single crystal structure of the cluster Au 144 (CCAr) 60 with a multishell structure, based on Mackay icosahedra. 21 Yan et al cocrystallized two alloyed clusters, that is, (AuAg) 267 (SR) 80 (1.65 nm) and (AuAg) 45 (SR) 27 (PPh 3 ) 6 (1.05−1.25 nm) and determined their structure by single-crystal X-ray diffraction. The larger cluster consists of four concentric icosahedral shells and has a fully metallic behavior (no band gap).…”

Section: ■ Introductionmentioning

confidence: 99%

Solution NMR Spectroscopy with Isotope-Labeled Cysteine (¹³C and ¹⁵N) Reveals the Surface Structure of l-Cysteine-Coated Ultrasmall Gold Nanoparticles (1.8 nm)

et al. 2018

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Ultrasmall gold nanoparticles with a diameter of 1.8 nm were synthesized by reduction of tetrachloroauric acid with sodium borohydride in the presence of l-cysteine, with natural isotope abundance as well as 13C-labeled and 15N-labeled. The particle diameter was determined by high-resolution transmission electron microscopy and differential centrifugal sedimentation. X-ray photoelectron spectroscopy confirmed the presence of metallic gold with only a few percent of oxidized Au(+I) species. The surface structure and the coordination environment of the cysteine ligands on the ultrasmall gold nanoparticles were studied by a variety of homo- and heteronuclear NMR spectroscopic techniques including 1H–13C-heteronuclear single-quantum coherence and 13C–13C-INADEQUATE. Further information on the binding situation (including the absence of residual or detached l-cysteine in the solution) and on the nanoparticle diameter (indicating the well-dispersed state) was obtained by diffusion-ordered spectroscopy (1H-, 13C-, and 1H-13C-DOSY). Three coordination environments of l-cysteine on the gold surface were identified that were ascribed to different crystallographic sites, supported by geometric considerations of the nanoparticle ultrastructure. The particle size data and the NMR-spectroscopic analysis gave a particle composition of about Au174(cysteine)67.

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Isolation and Total Structure Determination of an All‐Alkynyl‐Protected Gold Nanocluster Au₁₄₄

Cited by 46 publications

References 75 publications

Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles

Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles

Click Chemistry on the Surface of Ultrasmall Gold Nanoparticles (2 nm) for Covalent Ligand Attachment Followed by NMR Spectroscopy

Solution NMR Spectroscopy with Isotope-Labeled Cysteine (¹³C and ¹⁵N) Reveals the Surface Structure of l-Cysteine-Coated Ultrasmall Gold Nanoparticles (1.8 nm)

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Isolation and Total Structure Determination of an All‐Alkynyl‐Protected Gold Nanocluster Au144

Cited by 46 publications

References 75 publications

Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles

Insights into Interfaces, Stability, Electronic Properties, and Catalytic Activities of Atomically Precise Metal Nanoclusters from First Principles

Click Chemistry on the Surface of Ultrasmall Gold Nanoparticles (2 nm) for Covalent Ligand Attachment Followed by NMR Spectroscopy

Solution NMR Spectroscopy with Isotope-Labeled Cysteine (13C and 15N) Reveals the Surface Structure of l-Cysteine-Coated Ultrasmall Gold Nanoparticles (1.8 nm)

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Isolation and Total Structure Determination of an All‐Alkynyl‐Protected Gold Nanocluster Au₁₄₄

Solution NMR Spectroscopy with Isotope-Labeled Cysteine (¹³C and ¹⁵N) Reveals the Surface Structure of l-Cysteine-Coated Ultrasmall Gold Nanoparticles (1.8 nm)