Yuichi Negishi

Ubiquitous 8 and 29 kDa gold:alkanethiolate cluster compounds: mass-spectrometric determination of molecular formulas and structural implications.

The molecular formulas and charge state distributions of thus-far known ubiquitous alkanethiolate-protected gold clusters with core-masses of 8 and 29 kDa were assessed using electrospray ionization mass spectrometry. The 8 and 29 kDa clusters were determined to be composed of single species, [Au38(SCn)24]z and [Au144(SCn)59]z, respectively, with charge states of z >/= 0. Possible geometric structures for Au38(SCn)24 and Au144(SCn)59 are discussed, based on the structures of relevant systems that have been recently determined experimentally and theoretically: [Au25(SR)18]- and Au102(SR)44, in which the Au cores are protected by monomers [-SR-Au-SR-] and/or dimers [-SR-Au-SR-Au-SR-]. Their preferential formation and chemical robustness are proposed as being associated with high stability due to geometric factors, while the Au-thiolate interface takes on common motifs regardless of the underlying Au core.

Isolation, structure, and stability of a dodecanethiolate-protected Pd1Au24 cluster

A dodecanethiolate-protected Pd(1)Au(24)(SC(12)H(25))(18) cluster, which is a mono-Pd-doped cluster of the well understood magic gold cluster Au(25)(SR)(18), was isolated in high purity using solvent fractionation and high-performance liquid chromatography (HPLC) after the preparation of dodecanethiolate-protected palladium-gold bimetal clusters. The cluster thus isolated was identified as the neutral [Pd(1)Au(24)(SC(12)H(25))(18)](0) from the retention time in reverse phase columns and by elemental analyses. The LDI mass spectrum of [Pd(1)Au(24)(SC(12)H(25))(18)](0) indicates that [Pd(1)Au(24)(SC(12)H(25))(18)](0) adopts a similar framework structure to Au(25)(SR)(18), in which an icosahedral Au(13) core is protected by six [-S-Au-S-Au-S-] oligomers. The optical absorption spectrum of [Pd(1)Au(24)(SC(12)H(25))(18)](0) exhibits peaks at approximately 690 and approximately 620 nm, which is consistent with calculated results on [Pd(1)@Au(24)(SC(1)H(3))(18)](0) in which the central gold atom of Au(25)(SC(1)H(3))(18) is replaced with Pd. These results strongly indicate that the isolated [Pd(1)Au(24)(SC(12)H(25))(18)](0) has a core-shell [Pd(1)@Au(24)(SC(12)H(25))(18)](0) structure in which the central Pd atom is surrounded by a frame of Au(24)(SC(12)H(25))(18). Experiments on the stability of the cluster showed that Pd(1)@Au(24)(SC(12)H(25))(18) is more stable against degradation in solution and laser dissociation than Au(25)(SC(12)H(25))(18). These results indicate that the doping of a central atom is a powerful method to increase the stability beyond the Au(25)(SR)(18) cluster.

Evolution of Hierarchical Hexagonal Stacked Plates of CuS from Liquid-Liquid Interface and its Photocatalytic Application for Oxidative Degradation of Different Dyes under Indoor Lighting

Blue solution of copper(II) acetylacetonate complex, [Cu(acac)(2)] in dichloromethane (DCM) and an aqueous alkaline solution of thioacetamide (TAA) constitute a biphasic system. The system in a screw cap test tube under a modified hydrothermal (MHT) reaction condition produces a greenish black solid at the liquid-liquid interface. It has been characterized that the solid mass is an assembly of hexagonal copper sulfide (CuS) nanoplates representing a hierarchical structure. The as-synthesized CuS nanoplates are well characterized by several physical techniques. An ethanolic dispersion of CuS presents a high band gap energy (2.2 eV) which assists visible light photocatalytic mineralization of different dye molecules. Thus a cleanup measure of dye contaminated water body even under indoor light comes true.

A Critical Size for Emergence of Nonbulk Electronic and Geometric Structures in Dodecanethiolate-Protected Au Clusters

We report on how the transition from the bulk structure to the cluster-specific structure occurs in n-dodecanethiolate-protected gold clusters, Au(n)(SC12)m. To elucidate this transition, we isolated a series of Au(n)(SC12)m in the n range from 38 to ∼520, containing five newly identified or newly isolated clusters, Au104(SC12)45, Au(∼226)(SC12)(∼76), Au(∼253)(SC12)(∼90), Au(∼356)(SC12)(∼112), and Au(∼520)(SC12)(∼130), using reverse-phase high-performance liquid chromatography. Low-temperature optical absorption spectroscopy, powder X-ray diffractometry, and density functional theory (DFT) calculations revealed that the Au cores of Au144(SC12)60 and smaller clusters have molecular-like electronic structures and non-fcc geometric structures, whereas the structures of the Au cores of larger clusters resemble those of the bulk gold. A new structure model is proposed for Au104(SC12)45 based on combined approach between experiments and DFT calculations.

Silver Nanoparticle Decorated Reduced Graphene Oxide (rGO) Nanosheet: A Platform for SERS Based Low-Level Detection of Uranyl Ion

Herein, a simple wet-chemical pathway has been demonstrated for the synthesis of silver nanoparticle conjugated reduced graphene oxide nanosheets where dimethylformamide (DMF) is judiciously employed as an efficient reducing agent. Altogether, DMF reduces both silver nitrate (AgNO3) and graphene oxide (GO) in the reaction mixture. Additionally, the presence of polyvinylpyrolidone (PVP) assists the nanophasic growth and homogeneous distribution of the plasmonic nanoparticle Ag(0). Reduction of graphene oxide and the presence of aggregated Ag NPs on reduced graphene oxide (rGO) nanosheets are confirmed from various spectroscopic techniques. Finally, the composite material has been exploited as an intriguing platform for surface enhanced Raman scattering (SERS) based selective detection of uranyl (UO2(2+)) ion. The limit of detection has been achieved to be as low as 10 nM. Here the normal Raman spectral (NRS) band of uranyl acetate (UAc) at 838 cm(-1) shifts to 714 and 730 cm(-1) as SERS bands for pH 5.0 and 12.0, respectively. This distinguished Raman shift of the symmetric stretching mode for UO2(2+) ion is indicative of pronounced charge transfer (CT) effect. This CT effect even supports the higher sensitivity of the protocol toward UO2(2+) over other tested oxo-ions. It is anticipated that rGO nanosheets furnish a convenient compartment to favor the interaction between Ag NPs and UO2(2+) ion through proximity induced adsorption even at low concentration.

Effect of Copper Doping on Electronic Structure, Geometric Structure, and Stability of Thiolate-Protected Au25 Nanoclusters

Several recent studies have attempted to impart [Au25(SR)18](-) with new properties by doping with foreign atoms. In this study, we studied the effect of copper doping on the electronic structure, geometric structure, and stability of [Au25(SR)18](-) with the aim of investigating the effect of foreign atom doping of [Au25(SR)18](-). CunAu25-n(SC2H4Ph)18 was synthesized by reducing complexes formed by the reaction between metal salts (copper and gold salts) and PhC2H4SH with NaBH4. Mass analysis revealed that the products contained CunAu25-n(SC2H4Ph)18 (n = 1-5) in high purity. Experimental and theoretical analysis of the synthesized clusters revealed that copper doping alters the optical properties and redox potentials of the cluster, greatly distorts its geometric structure, and reduces the cluster stability in solution. These findings are expected to be useful for developing design guidelines for functionalizing [Au25(SR)18](-) through doping with foreign atoms.

Synthesis and the Origin of the Stability of Thiolate-Protected Au130 and Au187 Clusters

Two stable thiolate-protected gold clusters (Au-SR), Au130 and Au187 clusters, were synthesized to obtain a better understanding of the size dependence of the origin of the stability of Au-SR clusters. These clusters were synthesized by employing different preparation conditions from those used to synthesize previously reported magic gold clusters; in particular, a lower [RSH] to [AuCl4(-)] molar ratio ([AuCl4(-)]/[RSH] = 1:1) was used than that used to prepare Au25(SR)18, Au38(SR)24, Au68(SR)34, Au102(SR)44, and Au144(SR)60 (id. = 1:4-12). The two clusters thus synthesized were separated from the mixture by high-performance liquid chromatography with reverse-phase columns. Mass spectrometry of the products revealed the presence of two clusters with chemical compositions of Au130(SC12H25)50 and Au187(SC12H25)68. The origin of the stability of these two clusters and the size dependence of the origin of the stability of thiolate-protected gold clusters were discussed in terms of the total number of valence electrons.

A New Binding Motif of Sterically Demanding Thiolates on a Gold Cluster

A gold cluster, Au(41)(S-Eind)(12), was synthesized by ligating the bulky arenethiol 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacene-4-thiol (Eind-SH) to preformed Au clusters. Extended X-ray absorption fine structure, X-ray photoelectron spectroscopy, and the fragmentation pattern in the mass spectrometry analysis indicated that formation of gold-thiolate oligomers at the interface was suppressed, in sharp contrast to conventional thiolate-protected Au clusters.

Separation of Precise Compositions of Noble Metal Clusters Protected with Mixed Ligands

This report describes the precise and systematic synthesis of PdAu24 clusters protected with two types of thiolate ligands (-SR1 and -SR2). It involved high-resolution separation of metal clusters containing a distribution of chemical compositions, PdAu24(SR1)18-n(SR2)n (n = 0, 1, 2, ..., 18), to individual clusters of specific n using high-performance liquid chromatography. Similar high-resolution separation was achieved for a few ligand combinations as well as clusters with other metal cores, such as Au25 and Au38. These results demonstrate the ability to precisely control the chemical composition of two types of ligands in thiolate-protected mono- and bimetallic metal clusters. It is expected that greater functional control of thiolate-protected metal clusters, their regular arrays, and systematic variation of their properties can now be achieved.

Ligand-Induced Stability of Gold Nanoclusters: Thiolate versus Selenolate

Thiolate-protected gold nanoclusters have attracted considerable attention as building blocks for new functional materials and have been extensively researched. Some studies have reported that changing the ligand of these gold nanoclusters from thiolate to selenolate increases cluster stability. To confirm this, in this study, we compare the stabilities of precisely synthesized [Au25(SC8H17)18](-) and [Au25(SeC8H17)18](-) against degradation in solution, thermal dissolution, and laser fragmentation. The results demonstrate that changing the ligand from thiolate to selenolate increases cluster stability in reactions involving dissociation of the gold-ligand bond but reduces cluster stability in reactions involving intramolecular dissociation of the ligand. These results reveal that using selenolate ligands makes it possible to produce gold clusters that are more stable against degradation in solution than thiolate-protected gold nanoclusters.