Predictive Gold Nanocluster Formation Controlled by Metal‐Ligand Complexes

Pettibone, John M.; Hudgens, Jeffrey W.

doi:10.1002/smll.201101777

Cited by 32 publications

(25 citation statements)

References 45 publications

(88 reference statements)

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“…[ 2–6 ] Now, AuNCs have been recognized as a kind of promising nanomaterials owning to their spectroscopic properties, biological applications, catalytic properties, and etc. [ 7–13 ]…”

Section: Introductionmentioning

confidence: 99%

Understanding the Chemical Insights of Staple Motifs of Thiolate‐Protected Gold Nanoclusters

Wang

Zhu

et al. 2020

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Improving the fundamental understanding of the basic structures of ligand‐protected gold nanoclusters is essential to their bottom‐up synthesis as well as their further application explorations. The thiolate ligands that cover the central metal core in staple motifs are vital for the stability of the gold clusters. However, the knowledge about the geometrical and bonding characters of the thiolate ligands has not been fully uncovered yet. In this work, density functional theory calculations and molecular orbital analysis are applied to show that the Au atoms in the thiolate ligands are hypervalent. The chemical insights of the linear SAuS configuration as well as the lengthened AuS bond by combining the 3‐center 4‐electron (3c‐4e) model and the well‐recognized valence shell electron pair repulsion theory are revealed. Valence bond formulations of the motifs are given to provide more chemical insights, for example, the resonant structures, to show how the thiolate motif forms one covalent bond and one dative covalent bond with the Au core. This work provides a thorough understanding of the structure and bonding pattern of thiolate ligands of Au nanoclusters, which is important for the rational design of ligands‐protected Au nanoclusters.

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“…[ 2–6 ] Now, AuNCs have been recognized as a kind of promising nanomaterials owning to their spectroscopic properties, biological applications, catalytic properties, and etc. [ 7–13 ]…”

Section: Introductionmentioning

confidence: 99%

Understanding the Chemical Insights of Staple Motifs of Thiolate‐Protected Gold Nanoclusters

Wang

Zhu

et al. 2020

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“…[1][2][3][4][5][6] For both basic and application researches, the availability of well-defined nanoclusters is crucial, which depends critically on the design and implementation of solution-based synthetic chemistry. Good examples of this methodology are Au 25 nanorods converted from triphenylphosphine (PPh 3 )-protected polydisperse Au nanoparticles (1−3.5 nm) via one-pot thiol etching, 8,9 SR-protected Au 38 Good examples of this methodology are Au 25 nanorods converted from triphenylphosphine (PPh 3 )-protected polydisperse Au nanoparticles (1−3.5 nm) via one-pot thiol etching, 8,9 SR-protected Au 38 …”

Section: Introductionmentioning

confidence: 99%

In situ studies on controlling an atomically-accurate formation process of gold nanoclusters

et al. 2015

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Knowledge of the molecular formation mechanism of metal nanoclusters is essential for developing chemistry for accurate control over their synthesis. Herein, the "top-down" synthetic process of monodisperse Au13 nanoclusters via HCl etching of polydisperse Aun clusters (15 ≤ n ≤ 65) is traced by a combination of in situ X-ray/UV-vis absorption spectroscopy and time-dependent mass spectrometry. It is revealed experimentally that the HCl-induced synthesis of Au13 is achieved by accurately controlling the etching process with two distinctive steps, in sharp contrast to the traditional thiol-etching mechanism through release of the Au(i) complex. The first step involves the direct fragmentation of the initial larger Aun clusters into metastable intermediate Au8-Au13 smaller clusters. This is a critical step, which allows for the secondary size-growth step of the intermediates toward the atomically monodisperse Au13 clusters via incorporating the reactive Au(i)-Cl species in the solution. Such a secondary-growth pathway is further confirmed by the successful growth of Au13 through reaction of isolated Au11 clusters with AuClPPh3 in the HCl environment. This work addresses the importance of reaction intermediates in guiding the way towards controllable synthesis of metal nanoclusters.

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“…This study examined diphosphine ligands with alkyl chains containing one to six carbon atoms. [18] By using mass spectrometry they were able to track the evolution of different types of initial metal complexes into larger gold clusters. In a similar vein, detailed reaction pathways for the production of larger gold clusters from smaller clusters and the metal-ligand complexes that are formed initially in solution have been proposed for 1,5-bis(diphenylphosphino)pentane.…”

Section: Full Papersmentioning

confidence: 99%

Synthesis and Characterization of Gold Clusters Ligated with 1,3‐Bis(dicyclohexylphosphino)propane

2013

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In this multidisciplinary study the chemical reduction synthesis of novel gold clusters in solution was combined with high‐resolution analytical mass spectrometry (MS) to gain insight into the composition of the gold clusters and how their size, ionic charge state, and ligand substitution influences their gas‐phase fragmentation pathways. Ultrasmall cationic gold clusters ligated with 1,3‐bis(dicyclohexylphosphino)propane (dcpp) were synthesized for the first time and introduced into the gas phase using electrospray ionization (ESI). Mass‐selected cluster ions were fragmented by employing collision‐induced dissociation (CID) and the product ions were analyzed using MS. The solutions were found to contain the multiply charged cationic gold clusters Au9L43+, Au13L53+, Au6L32+, Au8L32+, and Au10L42+ (L=dcpp). The gas‐phase fragmentation pathways of these cluster ions were examined systematically by employing CID combined with MS. In addition, CID experiments were performed on related gold clusters of the same size and ionic charge state but capped with 1,3‐bis(diphenylphosphino)propane (dppp) ligands containing phenyl functional groups at the two phosphine centers instead of cyclohexane rings. It is shown that this relatively small change in the molecular substitution of the two phosphine centers in diphosphine ligands (C6H11 versus C6H5) exerts a pronounced influence on the size of the species that are preferentially formed in solution during reduction synthesis as well as the gas‐phase fragmentation channels of otherwise identical gold cluster ions. The mass spectrometry results indicate that in addition to the length of the alkyl chain between the two phosphine centers, the substituents at the phosphine centers also play a crucial role in determining the composition, size, and stability of diphosphine‐ligated gold clusters synthesized in solution.

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Predictive Gold Nanocluster Formation Controlled by Metal‐Ligand Complexes

Cited by 32 publications

References 45 publications

Understanding the Chemical Insights of Staple Motifs of Thiolate‐Protected Gold Nanoclusters

Understanding the Chemical Insights of Staple Motifs of Thiolate‐Protected Gold Nanoclusters

In situ studies on controlling an atomically-accurate formation process of gold nanoclusters

Synthesis and Characterization of Gold Clusters Ligated with 1,3‐Bis(dicyclohexylphosphino)propane

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