Thiolated Gold Nanoclusters Research Articles

Quantum sized, thiolate-protected gold nanoclusters

The scientific study of gold nanoparticles (typically 1-100 nm) has spanned more than 150 years since Faraday's time and will apparently last longer. This review will focus on a special type of ultrasmall (<2 nm) yet robust gold nanoparticles that are protected by thiolates, so-called gold thiolate nanoclusters, denoted as Au(n)(SR)(m) (where, n and m represent the number of gold atoms and thiolate ligands, respectively). Despite the past fifteen years' intense work on Au(n)(SR)(m) nanoclusters, there is still a tremendous amount of science that is not yet understood, which is mainly hampered by the unavailability of atomically precise Au(n)(SR)(m) clusters and by their unknown structures. Nonetheless, recent research advances have opened an avenue to achieving the precise control of Au(n)(SR)(m) nanoclusters at the ultimate atomic level. The successful structural determination of Au(102)(SPhCOOH)(44) and [Au(25)(SCH(2)CH(2)Ph)(18)](q) (q = -1, 0) by X-ray crystallography has shed some light on the unique atomic packing structure adopted in these gold thiolate nanoclusters, and has also permitted a precise correlation of their structure with properties, including electronic, optical and magnetic properties. Some exciting research is anticipated to take place in the next few years and may stimulate a long-lasting and wider scientific and technological interest in this special type of Au nanoparticles.

Mass Spectrometric Identification of Au68(SR)34 Molecular Gold Nanoclusters with 34-Electron Shell Closing

The molecular formula Au(68)(SCH(2)CH(2)Ph)(34) has been assigned to the 14 kDa nanocluster using MALDI-TOF mass spectrometry. The 34-electron shell closing in a macroscopically obtained thiolated gold nanocluster is demonstrated. The Au(68) nanocluster is predicted to have a 49 atom Marks decahedral core with 19 inner core atoms and 30 outer atoms chelating with the staple motifs. The nanoclusters' predicted formulation is [Au](19+30) [Au(SR)(2)](11) [Au(2)(SR)(3)](4).

Facile, large-scale synthesis of dodecanethiol-stabilized Au38 clusters.

It has long been a major challenge to achieve synthetic control over size and monodispersity of gold thiolate nanoclusters. Among the reported Aun thiolate clusters, Au38 has been shown to be particularly stable but was only obtained as a minor product in previous syntheses. In this work, we report a bulk solution synthetic method that permits large-scale, facile synthesis of truly monodisperse Au38 nanoclusters. This new method explores a two-phase ligand exchange process utilizing glutathione-capped Aun clusters as the starting material. The ligand exchange process with neat dodecanethiols causes gold core etching and secondary growth of clusters, and eventually leads to monodisperse Au38 clusters in high purity, which eliminates nontrivial postsynthetic separation steps. This method can be readily scaled up to synthesize Au38(SC12H25)24 in large quantities and thus makes the approach and Au38 nanoclusters of broad utility.