Tohoku University · Materials Science
Professor Yuichi Negishi's research lab specializes in the synthesis, isolation, and characterization of atomically precise thiolate-protected gold and gold-silver alloy clusters. The lab focuses on understanding the electronic and structural properties of these nanoscale materials through advanced analytical techniques such as electrospray ionization mass spectrometry, UV-Vis-NIR spectroscopy, X-ray diffraction, and DFT calculations. A central theme is elucidating the origins of magic-number stability and electronic shell closure in gold clusters, as well as exploring the tunable optical and electronic properties via alloying and size control. The lab also investigates the transition from molecular-like clusters to bulk-like structures in ligand-protected gold systems.
Figures are computed from collected data and may differ slightly.
Small gold clusters (approximately 1 nm) protected by molecules of a tripeptide, glutathione (GSH), were prepared by reductive decomposition of Au(I)-SG polymers at a low temperature and separated into a number of fractions by polyacrylamide gel electrophoresis (PAGE). Chemical compositions of the fractionated clusters determined previously by electrospray ionization (ESI) mass spectrometry (Negishi, Y. et al. J.Am. Chem. Soc. 2004, 126, 6518) were reassessed by taking advantage of freshly prepa
Small gold clusters (<1 nm) protected by a glutathione (GSH) monolayer were fractionated into six components by polyacrylamide gel electrophoresis, and their chemical compositions were investigated by electrospray ionization mass spectroscopy. The results demonstrate isolation of a series of magic-numbered gold clusters, Au18(SG)11, Au21(SG)12, Au25+/-1(SG)14+/-1, Au28(SG)16, Au32(SG)18, and Au39(SG)23. Their optical absorption spectra are highly structured with clear absorption onsets, which sh
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 o
The effect of Ag doping on the electronic structure of a stable thiolate-protected Au(25) cluster (Au(25)(SR)(18)) was studied by measuring the optical spectra of Au(25-n)Ag(n)(SC(12)H(25))(18) (n = 0-11) and the results reveal that the electronic structure of Au(25)(SC(12)H(25))(18) is sensitive to Ag doping and is continuously modulated by incorporation of Ag atoms.
The present work aims to test the validity of the electronic shell model for Au25(SC6H13)18 by monitoring the charge state of the Au:S core and thereby to elucidate the origin of magic stability. Electrospray ionization mass spectrometry revealed that the Schiffrin method yields [Au25(SC6H13)18]x with a distribution of charge states, which shifts toward negative values with reduction time. The stable ions [Au25(SC6H13)18]1+ and [Au25(SC6H13)18]1- can be synthesized by chemical oxidation and redu
Metal alloys exhibit functionalities unlike those of single metals. Such alloying has drawn considerable research interest, particularly for nanoscale particles (metal clusters/nanoparticles), from the viewpoint of creating new functional nanomaterials. In gas phase cluster research, generated alloy clusters can be spatially separated with atomic precision in vacuum. Thus, the influences of increases or decreases in each element on the overall electronic structure of the cluster can be elucidate
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 eleme
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
A phenylethanethiolate-protected Pd(2)Au(36)(SC(2)H(4)Ph)(24) cluster, which is a two-Pd atom-doped cluster of the well studied magic gold cluster Au(38)(SC(2)H(4)Ph)(24), was synthesized in high purity and its stability was investigated. The results demonstrate that Pd(2)Au(36)(SC(2)H(4)Ph)(24) is more stable than Au(38)(SC(2)H(4)Ph)(24) against degradation in solution and core etching by thiols.
We report herein a simple method to prepare subnanometer-sized gold clusters by the reactions between hydrogen tetrachloroaurate (HAuCl4) and meso-2,3-dimercaptosuccinic acid (DMSA; HO2CCH(SH)CH(SH)CO2H) in water. It is demonstrated that DMSA molecules efficiently reduce the Au(III) species and stabilize the resultant gold clusters. The Au:DMSA clusters, which tend to aggregate into assemblages in water, can be well-isolated from each other by ion-pair formation between the carboxyl groups of DM
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
We report herein the X-ray magnetic circular dichroism (XMCD) at the Au L2,3 edges of a series of Au clusters protected by glutathione (GSH). The samples used here included AuN(SG)M with (N, M) = (10, 10), (15, 13), (18, 14), (22, 16), (25, 18), (29, 20), (39, 24) and a sodium gold(I) thiomalate (SGT) as a reference. Magnetic moments per cluster were found to be increased with size, whereas those per Au-S bond were nearly constant. This finding suggests that a localized hole created by Au-S bond
To establish an ultimate energy conversion system consisting of a water-splitting photocatalyst and a fuel cell, it is necessary to further increase the efficiencies of the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), and the oxygen reduction reaction (ORR). Recently, it was demonstrated that thiolate (SR)-protected gold clusters, Aun(SR)m, and their related alloy clusters can serve as model catalysts for these three reactions. However, as the previous data have been o
Glutathione-protected Au25 clusters were used to load monodisperse gold nanoclusters (1.2 ± 0.3 nm) onto BaLa4Ti4O15 to create photocatalysts. The photocatalytic activity of the resulting material for water splitting was determined to be 2.6 times higher than that of catalysts loaded with larger gold nanoparticles (10-30 nm) via conventional photodeposition.
Open papers in the app to read, cite, and organize with AI.
