Ligand exchange is a fundamental reaction of metal nanoparticles. Multiple symmetry and kinetic exchange environments are observed for thiolate protected gold nanoparticles, but the correlation ...between these is unclear. Structural study of ligand exchange on chalcogenide passivated gold clusters has so-far revealed the locations of 10% or fewer of incoming ligands. In a set of 13 crystal structures, we reveal the locations of up to 17 ligands of the 18 ligands in thiolate for selenolate exchanged Au25(SeR)18–x (SR) x clusters. Overall, we see a distinct preference for the locations of thiolate and selenolate ligands that emerges over time. This most-comprehensive to-date structural study of ligand exchange on gold clusters evidences a structural basis for exchange of solvated ligands, exchange of ligands between clusters, and a net reaction that amounts to translation of ligands on the cluster surface.
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The Au102(pMBA)44 nanocluster becomes a superatom paramagnet after chemical oxidation. Solutions of paramagnetic Au102(pMBA)44 heat in an oscillating magnetic field component of an RF field, but not ...in the electric component. Combined, these experiments suggest that paramagnetic Au102(pMBA)44 heats through interactions of spin magnetic moment with an external oscillating magnetic field. These results may clarify some current controversy regarding gold nanoparticle heating in radiofrequency fields.
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Acetylide-protected gold nanoclusters represent a recently described class of nanocluster compounds that are computationally predicted to be more stable than well-studied thiolate-protected clusters. ...Ligand exchange of thiolates-for-acetylides on these clusters as well as the reverse reaction are so-far unknown. Such reactions can inform a practical understanding of stability and other differences between thiolate- and acetylide-protected gold clusters. Here it is shown that acetylide-for-thiolate ligand exchange is facile when using either a lithium phenylacetylide or a gold(
i
)-phenylacetylide complex as incoming ligand to thiolate-protected gold clusters, whereas the reaction fails when using phenylacetylene. Both partial and full exchange are possible, as is the reverse reaction. While the overall reaction resembles ligand exchange, it may be better described as a metathesis reaction. Notably, while the simple thiolate-for-acetylide exchange reaction is enthalpically unfavorable, metathesis reactions between these ligands are enthalpically favorable. Intercluster exchange is also observed between thiolate-protected and acetylide-protected clusters.
New ligand-exchange reactions are reported for thiolate- and acetylide-protected gold nanoclusters, which are rationalized through bond strengths and enthalpy arguments.
Structural information on nanometer-sized gold particles has been limited, due in part to the problem of preparing homogeneous material. Here we report the crystallization and x-ray structure ...determination of a p-mercaptobenzoic acid (p-MBA)-protected gold nanoparticle, which comprises 102 gold atoms and 44 p-MBAs. The central gold atoms are packed in a Marks decahedron, surrounded by additional layers of gold atoms in unanticipated geometries. The p-MBAs interact not only with the gold but also with one another, forming a rigid surface layer. The particles are chiral, with the two enantiomers alternating in the crystal lattice. The discrete nature of the particle may be explained by the closing of a 58-electron shell.
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Near-infrared photoluminescence of a series of three gold monolayer protected clusters (MPCs) with volumes spanning 50–200 Å3 was studied by using variable-temperature photoluminescence (VT-PL) ...spectroscopy. The three MPCs, which included Au20(SC8H9)15-diglyme, Au25(SC8H9)18, and Au38(SC12H25)24, all exhibited temperature-dependent intensities that reflected a few-millielectronvolt energy gap that separated bright emissive and dark nonradiative electronic states. All clusters showed increased PL intensities upon raising the sample temperature from 4.5 K to a cluster-specific value, upon which increased sample temperature resulted in emission quenching. The increased PL in the low-temperature range is attributed to thermally activated carrier transfer from dark to bright states. The quenching at elevated temperatures is attributed to nonradiative vibrational relaxation through Au–Au stretching of the MPCs metal core. Importantly, the results show evidence of a common and size scalable metal-centered intraband PL mechanism that is general for ultrasmall metal nanoclusters, which are expected to show nonscalable optical properties.
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Synthesis, characterization, and functionalization of self-assembled, ligand-stabilized gold nanoparticles are long-standing issues in the chemistry of nanomaterials. Factors driving the ...thermodynamic stability of well documented discrete sizes are largely unknown. Herein, we provide a unified view of principles that underlie the stability of particles protected by thiolate (SR) or phosphine and halide (PR₃, X) ligands. The picture has emerged from analysis of large-scale density functional theory calculations of structurally characterized compounds, namely Au₁₀₂(SR)₄₄, Au₃₉(PR₃)₁₄X₆⁻, Au₁₁(PR₃)₇X₃, and Au₁₃(PR₃)₁₀X₂³⁺, where X is either a halogen or a thiolate. Attributable to a compact, symmetric core and complete steric protection, each compound has a filled spherical electronic shell and a major energy gap to unoccupied states. Consequently, the exceptional stability is best described by a "noble-gas superatom" analogy. The explanatory power of this concept is shown by its application to many monomeric and oligomeric compounds of precisely known composition and structure, and its predictive power is indicated through suggestions offered for a series of anomalously stable cluster compositions which are still awaiting a precise structure determination.
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Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional ...methods for structure characterization. Here we present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. The study reveals structural polymorphism in these archetypal nanoclusters. In addition to confirming the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. The discovery of polymorphism may open up a new dimension in nanoscale engineering.
Etching of gold with an excess of thiol ligand is used in both synthesis and analysis of gold particles. Mechanistically, the process of etching gold with excess thiol is unclear. Previous studies ...have obliquely considered the role of oxygen in thiolate etching of gold. Herein, we show that oxygen or a radical initiator is a necessary component for efficient etching of gold by thiolates. Attenuation of the etching process by radical scavengers in the presence of oxygen, and the restoration of activity by radical initiators under inert atmosphere, strongly implicate the oxygen radical. These data led us to propose an atomistic mechanism in which the oxygen radical initiates the etching process.
A radical new insight: The final step in the synthesis of atomically defined gold clusters has remained mechanistically obscure. A thiol‐induced etching step is proposed that is initiated by the oxygen diradical.
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Ligand exchange reactions are widely used for imparting new functionality on or integrating nanoparticles into devices. Thiolate-for-thiolate ligand exchange in monolayer protected gold nanoclusters ...has been used for over a decade; however, a firm structural basis of this reaction has been lacking. Herein, we present the first single-crystal X-ray structure of a partially exchanged Au102(p-MBA)40(p-BBT)4 (p-MBA = para-mercaptobenzoic acid, p-BBT = para-bromobenzene thiol) with p-BBT as the incoming ligand. The crystal structure shows that 2 of the 22 symmetry-unique p-MBA ligand sites are partially exchanged to p-BBT under the initial fast kinetics in a 5 min timescale exchange reaction. Each of these ligand-binding sites is bonded to a different solvent-exposed Au atom, suggesting an associative mechanism for the initial ligand exchange. Density functional theory calculations modeling both thiol and thiolate incoming ligands postulate a mechanistic pathway for thiol-based ligand exchange. The discrete modification of a small set of ligand binding sites suggests Au102(p-MBA)44 as a powerful platform for surface chemical engineering.
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The Au102(p-MBA)44 cluster (p-MBA: para-mercaptobenzoic acid) is observed as a chiral compound comprised of achiral components in its single-crystal structure. So far the enantiomers observed in the ...crystal structure are not isolated, nor is the circular dichroism spectrum known. A chiral phase transfer method is presented which allows partial resolution of the enantiomers by the use of a chiral ammonium bromide, (−)-1R,2S-N-dodecyl-N-methylephedrinium bromide ((−)-DMEBr). At sufficiently low concentration of (−)-DMEBr, the phase transfer from water to chloroform is incomplete. Both the aqueous and organic phases show optical activity of near mirror image relationship. Differences in the spectra are ascribed to the formation of diastereomeric salts. At high concentrations of (−)-DMEBr, full phase transfer is observed. The organic phase, however, still displays optical activity. We assume that one of the diastereomers has very strong optical activity, which overrules the cancelation of the spectra with opposite sign. Comparison with computations further corroborates the experimental data and allows a provisional assignment of handedness of each fraction.
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