Intramolecular Metal Exchange Reaction Promoted by Thiol Ligands

Abstract

The synthesis of an alloy nanocluster that is atomically precise is the key to understanding the metal synergy effect at the atomic level. Using the Ag2Au25(SR)18 nanocluster as a model, we reported a third approach for the metal exchange reaction, that is, intramolecular metal exchange. The surface adsorbed metal ions (i.e., Ag) can be exchanged with the kernel metal atoms (i.e., Au) that are promoted by thiol ligands. The exchanged gold atoms can be further stripped by the thiol ligands, and produce the AgxAu25−x(SR)18− nanocluster.

Dynamics of Pd Dopant Atoms inside Au Nanoclusters during Catalytic CO Oxidation

“… 24 Metal migration in Ag 2 Au 25 clusters was found to occur also intramolecularly when exposed to a thiol solution. 25 Altogether, this demonstrated that in solution, the structure of doped nanoclusters is not static but evolves under different conditions.…”

Creation of active water-splitting photocatalysts by controlling cocatalysts using atomically precise metal nanoclusters

“…Under particular reaction conditions, such metal exchange does not occur, and another type of metal atoms or metal ions are deposited on the surface of the metal NCs (deposition of metal atoms/ions; Figure 5F). 184,200,201 In these synthetic methods, the method shown in Figure 5A is superior for systematically isolating a series of metal NCs, and the method shown in Figure 5B−F is superior for size-selectively synthesizing a specific metal NC. In addition to these methods, there have been several…”

Supramolecular Gold Chemistry: From Atomically Precise Thiolate-Protected Gold Nanoclusters to Gold-Thiolate Nanostructures

“…The aim of this Special Issue on "Supramolecular Gold Chemistry" was to provide a unique international forum aimed at covering a broad description of results involving the supramolecular chemistry of gold with a special focus on the gold-sulfur interface leading to hybrid materials, ranging from gold-thiolate complexes, [3] to thiolate-protected gold nanoclusters [4][5][6][7][8][9][10][11] and gold-thiolate supramolecular assemblies or nanoparticles. [12][13][14] The role of thiolates on the structure and optical features of gold nanohybrid systems (ranging from plasmonic gold nanoparticles and fluorescent gold nanoclusters to self-assembled Au-containing thiolated coordination polymers) has been highlighted in the review article by Csapó and coworkers [14].…”

“…Innovative strategies include a metal exchange reaction that leads to a new cluster compound in particular alloy nanoclusters. Zhu and coworkers describe a new type of metal exchange: self-alloying induced by intramolecular metal exchange, to produce the Ag x Au 25−x (SR) 18 − nanocluster [4]. Moreover, new synthetic routes, beyond wet chemistry using a reducing agent, are being explored.…”