Galvanic replacement-induced introduction of a heteroligand into bimetallic and trimetallic nanoclusters

Abstract

Heteroleptic eight-electron silver-rich alloy nanoclusters, [Au@Au4Ag12(dtp)7(PPh3)4]2+ (1), and [Pt@Au4Ag11(dtp)7(PPh3)4] (2) were successfully synthesized via galvanic-replacement reaction of 1,1-dithiolate-protected M@Ag20 (M = Au, Pt) nanoclusters with Au(I)-phosphine salts leading to the...

Recent progress in dichalcophosphate coinage metal clusters and superatoms

“…13). 106 Because the starting clusters do not react with Ph 3 P, it was assumed that the PPh 3 ligands enter the surface shell only after the metal exchange has taken place. The Au@Au 4 Ag 12 cluster has ideal C 2 symmetry and can be viewed as an Au-centred Au 4 Ag 8 icosahedron capped by four silver atoms (Fig.…”

“…105 More recently, another rare case where the metal exchange alters the cluster nuclearity was described. 106 The reaction of [Au@Ag 20 (dtp) 12 ] + and [Pt@Ag 20 (dtp) 12 ] with 4 equiv. of Au(PPh 3 )Cl resulted in eight-electron alloy nanoclusters [Au@Au 4 Ag 12 (dtp) 7 (PPh 3 ) 4 ] 2+ and [Pt@Au 4 Ag 11 (dtp) 7 (PPh 3 ) 4 ], respectively (Fig.…”

“…Fig. 13 Genesis and core structures of nanoalloys [Au@Au 4 Ag 12 -(dtp) 7 (PPh 3 ) 4 ] 2+ and [Pt@Au 4 Ag 11 (dtp) 7 (PPh 3 ) 4 ] 106. …”

Triplet–triplet annihilation-based photon upconversion using nanoparticles and nanoclusters

“…Similar to other ligand-protected metal nanoclusters, the electronic structure of rod-Au 25 can be modified by substituting different metal atoms. [94][95][96][97][98][99][100][101][102][103][104][105] Alloyed rod-Au 25Àx Ag x exhibits unique properties; for 0 r x r 12, the photoluminescence quantum yield is low, but at x = 13, there is a sudden and significant increase, approximately 200-fold. 106 Mitsui and colleagues conducted TTA-UC analysis of rod-Au 25Àx Ag x /perylene, revealing the following key findings: (1) photoluminescence from Au 25Àx Ag x is phosphorescent, (2) x = 12 may have the same high photoluminescence quantum yield as x = 13, and (3) substituting Ag atoms in the connecting part of the icosahedral core results in a higher energy shift of the triplet energy and enhancement of phosphorescence.…”

An Au5Ag12(SR)9(dppf)4 alloy nanocluster: structural determination and optical property and photothermal conversion investigation

“…50,51 This approach not only contributes to the scientific understanding of nanomaterials but also paves the way for the development of more efficient and versatile photothermal agents. In recent years, a variety of alloy nanoclusters, including the families of M 15 , 29,52,53 M 16 , 54,55 and M 17 , 56,57 have been synthesized, laying the groundwork for further investigation into the properties of clusters.…”