X-ray Crystal Structure and Optical Properties of Au_38–xCu_x(2,4-(CH₃)₂C₆H₃S)₂₄ (x = 0–6) Alloy Nanocluster

Abstract

In this work, we report the synthesis and crystal structure of Au38–x ­Cu x ­(2,4-DMBT)24 (x = 0–6, 2,4-DMBTH = 2,4-dimethyl­benzene­thiol) alloy nanocluster for the first time. A variety of characterizations including ESI-MS, TGA, and XPS reveal the composition as Au38–x ­Cu x ­(2,4-DMBT)24 (x = 0–6). The single crystal structure has been determined by an X-ray single crystal diffractometer. From the anatomy of the structure, a bi-icosahedral Au23 core is protected by six dimeric [−SR–M–SR–M–SR−] units (M = Cu/Au) and three monomeric [−SR–Au–SR−] units. It is interesting that all the Cu atoms are selectively doped in the motifs of the Au38–x ­Cu x ­(2,4-DMBT)24 nanocluster. This phenomenon is distinct from the exclusive core doping of the Ag atoms in the previously reported Au38–x ­Ag x alloy. Both the experimental results and DFT calculations of UV–vis spectra imply that the optical property of the Au38–x ­Cu x ­(2,4-DMBT)24 nanocluster is consistent with that of the Au38­(2,4-DMBT)24 nanocluster, because the Cu dopants make little contribution to the frontier orbitals of the alloy NC.

Atomically Precise Alloy Nanoclusters

“…9 (SR) 60 ] 0 are the main products. [159] [Au 38 (SR) 24 ] 0 is regarded as at ypeo fm agic Au NC, [159] and many alloy NCs [38,72,93,[160][161][162][163][164][165] However,a mong these NCs, only the geometricals tructures of [Au 38Àx Ag x (PET) 24 ] 0 and [Au 38Àx Cu x (2,4-SPhMe 2 ) 24 ] 0 have been determined by SC-XRD. [163,165] Figures Figure 1A 24 ] 0 (x = 1-3).…”

“…[159] [Au 38 (SR) 24 ] 0 is regarded as at ypeo fm agic Au NC, [159] and many alloy NCs [38,72,93,[160][161][162][163][164][165] However,a mong these NCs, only the geometricals tructures of [Au 38Àx Ag x (PET) 24 ] 0 and [Au 38Àx Cu x (2,4-SPhMe 2 ) 24 ] 0 have been determined by SC-XRD. [163,165] Figures Figure 1A 24 ] 0 (x = 1-3). [156][157][158] Reproducedw ith permission from references [156]- [158].Copyright 2016 Royal Society of Chemistry, Copyright 2019 American Chemical Society,a nd Copyright 2018 RoyalS ociety of Chemistry.…”

Exposing the Delocalized Cu−S π Bonds on the Au24Cu6(SPhtBu)22 Nanocluster and Its Application in Ring‐Opening Reactions

“…[28,29] Similar observations were observed in as eries of Au-Cu alloy nanoclusters reported by our group. [30,31] In ac ontinuation of these studies,w eu se the gold and copper salts to prepare new Au-Cu alloy nanoclusters that bear catalytically active Cu atoms on the surface.This could give rise to peripheral Culigand motifs,which are expected to facilitate novel catalytic reactions.…”

“…After the optimization of catalytic conditions (Supporting Information, Figures S13, S14), the catalytic activity of the Au 24 Cu 6 was tested. Forc omparison, the capacity of other nanoclusters (including the popular Au 25 , [34] and the alloy Au 38Àx Cu x , [31] and Ag 28 Cu 12 [35] nanoclusters) were also tested for the same reaction. NMR analysis was used to analyze the product ( Supporting Information, Figures S15, S16).…”

Exposing the Delocalized Cu−S π Bonds on the Au24Cu6(SPhtBu)22 Nanocluster and Its Application in Ring‐Opening Reactions

“…After the optimization of catalytic conditions (Supporting Information, Figures S13, S14), the catalytic activity of the Au 24 Cu 6 was tested. For comparison, the capacity of other nanoclusters (including the popular Au 25 , and the alloy Au 38− x Cu x , and Ag 28 Cu 12 nanoclusters) were also tested for the same reaction. NMR analysis was used to analyze the product (Supporting Information, Figures S15, S16).…”