Mono-cadmium vs Mono-mercury Doping of Au₂₅ Nanoclusters

Abstract

Controlling the dopant type, number, and position in doped metal nanoclusters (nanoparticles) is crucial but challenging. In the work described herein, we successfully achieved the mono-cadmium doping of Au25 nanoclusters, and revealed using X-ray crystallography in combination with theoretical calculations that one of the inner-shell gold atoms of Au25 was replaced by a Cd atom. The doping mode is distinctly different from that of mono-mercury doping, where one of the outer-shell Au atoms was replaced by a Hg atom. Au24Cd is readily transformed to Au24Hg, while the reverse (transformation from Au24Hg to Au24Cd) is forbidden under the investigated conditions.

Observation of gold sub-nanocluster nucleation within a crystalline protein cage

“…The Cd atom stabilizes the Au sub-nanocluster by forming the Au 3 Cd unit as described previously (Supplementary Fig. 3)414243. The Au clustering site at the three-fold channel was modelled based on the observed anomalous difference Fourier density map (Fig.…”

Switching a Nanocluster Core from Hollow to Nonhollow

“…The typical routes for metal NC synthesis are: i) direct reduction of metal precursors in the presence of desired ligands, [22][23][24][25][26][27][28] ii) postsynthetic ligand-exchange (LE), [29][30][31][32][33][34][35] and iii) metal-exchange 15,[36][37][38][39][40][41] . Among these methods, LE has recently been widely adopted for preparing novel gold NCs [42][43][44] .…”

Identification of an Eight-Electron Superatomic Cluster and Its Alloy in One Co-crystal Structure

“…So far, a variety of atom-precise Au-based alloy NCs have been reported. Especially, the doping of Au 25 (SR) 18 clusters was extensively studied with metals such as Cu [5], Pd [6], Pt [6], Ag [5,7], Cd [8], and Hg [9] and the results imply that Pd, Pt, and Cd atoms preferentially occupy the inner icosahedral positions, Ag resides on the surface of the superatomic core whereas Cu and Hg are found in the staple motifs. On the other hand reports on silver alloy NCs are comparatively scarce.…”