The mechanism of metal exchange in non-metallic nanoclusters

Abstract

We substituted gold atoms in fcc structured Au28 and Au36 nanoclusters with a Ag(i)SR complex and obtained AgxAu28−x and AgxAu36−x nanoclusters, respectively.

Dynamic Metal Exchange between a Metalloid Silver Cluster and Silver(I) Thiolate

“…For instance, the Ag atoms doped into Au 25 (PET) 18 prefer to occupy the surface of the icosahedral M 13 kernel, but the surface Au 2 (PET) 3 structure is difficult to dope. ,, In addition, the Au heteroatoms can also be introduced to specific sites of the Ag 44 (SR) 30 framework . Although the precise alloying process as well as the corresponding energy barriers remains unclear, the introduced heteroatoms should occupy the sites with the lowest energies or the lowest surface electrostatic potential . Nevertheless, several other questions remain unanswered: Could all sites in the cluster framework be doped?…”

“…Scientific research on metalloid clusters has a long history, and significant efforts have been made on manipulation over the structures (e.g., metal doping and ligand exchange) and the properties (e.g., optical and catalytic properties) of nanoparticles. − However, research on metalloid clusters has generally focused on structure determination and property investigations, while analysis on interactions between a metalloid cluster and foreign species just began to receive attention in the past decade. − Previous studies on such interactions mainly include the following two aspects: (i) the metal exchange process between a metalloid cluster (as precursors) and heterometal (representing a different metal element from the metalloid cluster) thiolate in the environment ,− and (ii) the intercluster reactions between different types of metalloid clusters in the same environment. − Specifically, for the metal exchange process, heterometal substitution is always determined by the relative energies of the doping sites and the characteristic of heterometals because of their different electron affinities. In this context, a fundamental understanding of the interaction between a metalloid cluster and the homometal thiolate still remains challenging.…”

Controlling ultrasmall gold nanoparticles with atomic precision

“…Recently, Zhu et al carefully investigated the Ag doping position of TBBT-protected Au 28 and Au 36 NCs by reacting with the Ag(I)SR complex. 94 Compared with the general doping of Ag atoms in the isotropic nanocluster (e.g., Au 25 (SR) 18 ), only specic Au atoms of Au 28 and Au 36 (e.g., Au atoms at the vertex sites in the metal core or in the staples) can be replaced by Ag atoms, which was attributed to the electrophilic effect revealed by DFT calculations. ) formed when the Cd-PET complex and Cd(PPh 3 ) 2 (NO 3 ) 2 were used as the ion precursor, respectively.…”

“…Recently, Zhu et al carefully investigated the Ag doping position of TBBT-protected Au 28 and Au 36 NCs by reacting with the Ag( i )SR complex. 94 Compared with the general doping of Ag atoms in the isotropic nanocluster ( e.g. , Au 25 (SR) 18 ), only specific Au atoms of Au 28 and Au 36 ( e.g.…”

Isotopic Exchange of Atomically Precise Nanoclusters with Materials of Varying Dimensions: From Nanoscale to Bulk

“…One of the growing areas of research is exploring the chemical reactions of these NCs . Ligand exchange − and metal exchange ,− reactions of NCs have been explored by various research groups. Intercluster reactions have established that NCs can react just as molecules. ,, Au 25 (SR) 18 – and Ag 44 (SR) 30 4– (SR is a thiolate ligand) react spontaneously to form alloy NCs as the product .…”