Superatom electron shell and/or geometric shell filling underlies the thermodynamic stability of coinage and alkali metal clusters in both theoretical and experimental results. Factors beyond simple shell filling contribute substantially to the lifetime of ligated clusters in solution. Such factors include the nature of the solvent, the atmosphere and the steric size of the ligand shell. Here we systematically lay out a ‘practical’ stability model for ligated metal clusters, which includes both shell-closing aspects and colloidal stability aspects. Cluster decomposition may follow either fusion or fission pathways. Solvent polarity can be determinative of the decomposition pathway.

The relationship between oxidation state, structure, and magnetism in many molecules is well described by first-order Jahn–Teller distortions. This relationship is not yet well defined for ligated nanoclusters and nanoparticles, especially the nano-technologically relevant gold-thiolate protected metal clusters. Here we interrogate the relationships between structure, magnetism, and oxidation state for the three stable oxidation states, −1, 0 and +1 of the thiolate protected nanocluster Au25(SR)18. We present the single crystal X-ray structures of the previously undetermined charge state Au25(SR)18+1, as well as a higher quality single crystal structure of the neutral compound Au25(SR)180. Structural data combined with SQUID magnetometry and DFT theory enable a complete description of the optical and magnetic properties of Au25(SR)18 in the three oxidation states. In aggregate the data suggests a first-order Jahn–Teller distortion in this compound. The high quality single crystal X-ray structure enables an analysis of the ligand–ligand and ligand–cluster packing interactions that underlie single-crystal formation in thiolate protected metal clusters.

The single-crystal X-ray structure of Pd-doped Au25(SR)18 was solved. The crystal structure reveals that in PdAu24(SR)18, the Pd atom is localized only to the centroid of the Au25(SR)18 cluster. This single-crystal X-ray structure shows that PdAu24(SR)180 is well conceptualized with the superatom theory. The PdAu24(SR)180 charge state is isoelectronic with Au25(SR)18+1 as determined by a first order Jahn–Teller effect of similar magnitude and by electrochemical comparison. The previously reported increased stability of PdAu24(SR)18 can be rationalized in terms of Pd–Au bonds that are shorter than the Au–Au bonds in Au25(SR)18.

The presence of oxygen in thiolate-protected gold nanoparticle synthesis influences product distribution. Oxygen’s diradical nature underlies this effect, and oxygen can be replaced with radical initiators in the synthesis of organosoluble gold nanoclusters. The role of O2 in the synthesis of water-soluble clusters such as Au102(p-MBA)44, Au25(SR)18, as well as the thiol etching of water-soluble colloidal gold particles is not yet established. Herein it is shown that radicals, either from O2 or from radical initiators such as 4-hydroxy-TEMPO, are necessary components for synthesis of water-soluble thiolate-protected gold nanoclusters, as well as the etching of aqueous colloidal gold by thiols. Furthermore, air-free synthetic routes to water-soluble gold nanoclusters Au102(SR)44 and Au25(SR)18 are described. Overall, the understanding of the role of radicals in the synthesis of water-soluble gold clusters will allow standardization of often difficult to reproduce syntheses that attract increasing attention for biological applications.

Pseudomonas moraviensis stanleyae was recently isolated from the roots of the selenium (Se) hyperaccumulator plant Stanleya pinnata. This bacterium tolerates normally lethal concentrations of SeO32− in liquid culture, where it also produces Se nanoparticles. Structure and cellular ultrastructure of the Se nanoparticles as determined by cellular electron tomography shows the nanoparticles as intracellular, of narrow dispersity, symmetrically irregular and without any observable membrane or structured protein shell. Protein mass spectrometry of a fractionated soluble cytosolic material with selenite reducing capability identified nitrite reductase and glutathione reductase homologues as NADPH dependent candidate enzymes for the reduction of selenite to zerovalent Se nanoparticles. In vitro experiments with commercially sourced glutathione reductase revealed that the enzyme can reduce SeO32− (selenite) to Se nanoparticles in an NADPH-dependent process. The disappearance of the enzyme as determined by protein assay during nanoparticle formation suggests that glutathione reductase is associated with or possibly entombed in the nanoparticles whose formation it catalyzes. Chemically dissolving the nanoparticles releases the enzyme. The size of the nanoparticles varies with SeO32− concentration, varying in size form 5 nm diameter when formed at 1.0 μM [SeO32−] to 50 nm maximum diameter when formed at 100 μM [SeO32−]. In aggregate, we suggest that glutathione reductase possesses the key attributes of a clonable nanoparticle system: ion reduction, nanoparticle retention and size control of the nanoparticle at the enzyme site.

Gold nanoparticle catalysis of chemical transformations has emerged as a subject of intense interest over the past decade. In particular, Au25(SR)18 has emerged as a model catalyst. In an effort to investigate their potential as intact, homogeneous, unsupported catalysts, we have discovered that Au25(SR)18 clusters are not stable in oxidizing conditions reported for catalytic styrene oxidation. Further investigation suggests that the active catalytic species is an Au(I) species resulting from oxidative decomposition of the starting gold cluster. This conclusion appears independent of R-group on thiolate-ligated Au25(SR)18 clusters.

We report the assembly of gold nanoclusters by the nonthiolate ligand diglyme into discrete and dynamic assemblies. To understand this surprising phenomenon, the assembly of Au20(SC2H4Ph)15-diglyme into Au20(SC2H4Ph)15-diglyme-Au20(SC2H4Ph)15 is explored in detail. The assembly is examined by high-angle annular dark field scanning transmission electron microscopy, size exclusion chromatography, mass spectrometry, IR spectroscopy, and calorimetry. We establish a dissociation constant for dimer to monomer conversion of 20.4 μM. Theoretical models validated by transient absorption spectroscopy predict a low-spin monomer and a high-spin dimer, with assembly enabled through weak diglyme oxygen–gold interactions. Close spatial coupling allows electron delocalization between the nanoparticle cores. The resulting assemblies thus possess optical and electronic properties that emerge as a result of assembly.Keywords: diglyme; dynamic assembly; gold nanoclusters; transient absorption spectroscopy;

This feature article reviews the thermal dissipation of nanoscopic gold under radiofrequency (RF) irradiation. It also presents previously unpublished data addressing obscure aspects of this phenomenon. While applications in biology motivated initial investigation of RF heating of gold nanoparticles, recent controversy concerning whether thermal effects can be attributed to nanoscopic gold highlight the need to understand the involved mechanism or mechanisms of heating. Both the nature of the particle and the nature of the RF field influence heating. Aspects of nanoparticle chemistry which may affect thermal dissipation include the hydrodynamic diameter of the particle, the oxidation state and related magnetism of the core, and the chemical nature of the ligand shell. Aspects of RF which may affect thermal dissipation include power, frequency and antenna designs that emphasize relative strength of magnetic or electric fields. These nanoparticle and RF properties are analysed in the context of three heating mechanisms proposed to explain gold nanoparticle heating in an RF field. This article also makes a critical analysis of the existing literature in the context of the nanoparticle preparations, RF structure, and suggested mechanisms in previously reported experiments.

The single-crystal X-ray structure of Au25(SC2H4Ph)16(pBBT)2 is presented. The crystallized compound resulted from ligand exchange of Au25(SC2H4Ph)18 with pBBT as the incoming ligand, and for the first time, ligand exchange is structurally resolved on the widely studied Au25(SR)18 compound. A single ligand in the asymmetric unit is observed to exchange, corresponding to two ligands in the molecule because of the crystallographic symmetry. The ligand-exchanged Au25 is bonded to the most solvent-exposed Au atom in the structure, making the exchange event consistent with an associative mechanism. The apparent nonexchange of other ligands is rationalized through possible selective crystallization of the observed product and differential bond lengths.

Etching or size-focusing methods are now widespread for preparation of atomically monodisperse thiolate-protected gold nanoparticles. Size-focusing methods are not widespread, however, in the production of water-soluble gold nanoparticles. Reported here is a new method for size-focusing of large gold nanoparticles utilizing p-mercaptobenzoic acid. We observe preferential formation of three large gold nanoparticles with approximate masses of 23, 51, and 88 kDa. On the basis of the stability of these masses against further etching or growth, they appear to be especially stable sizes. These sizes are not prominent after etching challenges with organosoluble ligands, and the 51 and 88 kDa sizes appear to be novel stable thiolate-protected gold cluster sizes. The overall trend in particle size distribution over time is also unusual, with larger sizes dominating at longer time points.

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.Keywords: gold nanoclusters; gold nanoparticles; hyperthermal therapy; radiofrequency

The exceptional stability of ligand-stabilized gold nanoclusters such as Au25(SC6H13)18–, Au39(PR3)14X6–, and Au102(SR)44 arises from the total filling of superatomic electron shells, resulting in a “noble-gas superatom” electron configuration. Electrochemical manipulation of the oxidation state can add or remove electrons from superatom orbitals, creating species electronically analogous to atomic radicals. Herein we show that oxidizing the Au25(SR)18– superatom from the noble-gas-like 1S21P6 electron configuration to the open-shell radical 1S21P5 and diradical 1S21P4 configurations results in decreased thermal stability of the compound, as measured by differential scanning calorimetry. Similar experiments probing five oxidation states of the putatively geometrically stabilized Au144(SR)60 cluster suggest a more complex relationship between oxidation state and thermal stability for this compound.

A method for estimating the positional displacement of protein bound gold nanoparticles is presented and used to estimate the rigidity of linkage of Au144 nanoparticles bound to a tetrameric model protein. We observe a distribution of displacement values where most Au144 clusters are immobilized to within 3 Å relative to the protein center of mass. The shape of the distribution suggests two physical processes of thermal motion and protein deformation. The application of this and similar rigid gold nanoparticle/protein conjugates in high resolution single particle electron cryo-microscopy is discussed.

Gold nanoparticle catalysis of chemical transformations has emerged as a subject of intense interest over the past decade. In particular, Au25(SR)18 has emerged as a model catalyst. In an effort to investigate their potential as intact, homogeneous, unsupported catalysts, we have discovered that Au25(SR)18 clusters are not stable in oxidizing conditions reported for catalytic styrene oxidation. Further investigation suggests that the active catalytic species is an Au(I) species resulting from oxidative decomposition of the starting gold cluster. This conclusion appears independent of R-group on thiolate-ligated Au25(SR)18 clusters.

The relationship between oxidation state, structure, and magnetism in many molecules is well described by first-order Jahn–Teller distortions. This relationship is not yet well defined for ligated nanoclusters and nanoparticles, especially the nano-technologically relevant gold-thiolate protected metal clusters. Here we interrogate the relationships between structure, magnetism, and oxidation state for the three stable oxidation states, −1, 0 and +1 of the thiolate protected nanocluster Au25(SR)18. We present the single crystal X-ray structures of the previously undetermined charge state Au25(SR)18+1, as well as a higher quality single crystal structure of the neutral compound Au25(SR)180. Structural data combined with SQUID magnetometry and DFT theory enable a complete description of the optical and magnetic properties of Au25(SR)18 in the three oxidation states. In aggregate the data suggests a first-order Jahn–Teller distortion in this compound. The high quality single crystal X-ray structure enables an analysis of the ligand–ligand and ligand–cluster packing interactions that underlie single-crystal formation in thiolate protected metal clusters.