Insights into mechanisms of diphosphine-mediated controlled surface construction on Au nanoclusters

Abstract

Unraveling the rules governing the size regulation of nanoclusters is of great importance not only in fundamental research, but also in practical applications because of the high structure-property correlation in...

The one/two atom size-reduction of [Au23SCy16]−induced by the [Au6(dppp)4]2+cluster

“…Of note, the UV-vis spectra of the formed Au clusters in this study is distinct from the reported one (+2 vs. 0). Besides, the Au 21 cluster co-protected by SCy and dppp ligands was not reported, 30 and the etching of Au 23 with Au I dppp generates Au 22 cluster exclusively in the early study. Herein, using Au 6 as a dppp-donating reagent, the Au 21 cluster co-protected by SCy and dppp ligand was gained as a main product.…”

“…The addition of different thiolate ligands (TBBzT/TBBT/2-NPT) results in the size-growth of Au 23 to Au 24 /Au 25 /Au 28 , 27,28 while the addition of phosphine ligand results in a distinct size-reduction of Au 23 → Au 22 (ref. 29 and 30)/Au 21 . 30 Meanwhile, the addition of MSCy (M = Ag/Au) complexes results in the formation of heavily Ag-doped alloy (AuAg) 25 31 and Au 28 , 32 respectively.…”

“…17 Of note, the inter-cluster reactions between two structurally distinct clusters have also been reported. In the pioneering studies, the reaction of [Au 25 (FTP) 30 Meanwhile, the addition of MSCy (M = Ag/Au) complexes results in the formation of heavily Ag-doped alloy (AuAg) 25 31 and Au 28 , 32 respectively. Of note, the Au 23 / Au 28 conversion has also been regulated by oxidation 33 and photooxidation 34 conditions.…”

Recent developments in the investigation of driving forces for transforming coinage metal nanoclusters

“…The reactivities of metal nanoclusters are fundamental in analyzing structural evolution, tailoring physicochemical properties, and promoting practical applications. Specifically, owing to their high reactivities, cluster-based functional nanomaterials have mutable and regulatable characteristics since nanocluster templates are easily modified with external conditions (acting as transforming driving forces), such as ligand exchange, [39][40][41][42] metal exchange, [43][44][45] redox, [46][47][48][49][50] and photo/temperature/pH variation [51][52][53] (Scheme 1). Accordingly, several cluster-based functional nanomaterials with unique features (such as enhanced stability, high sensitivity, or fast dynamic response) have been prepared for practical applications.…”

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

“…A recent study reports the successful introduction of diphosphine ligands onto the cluster surface by adding Au–diphosphine complexes to a thiolate-protected Au NC, [Au 23 (SR) 16 ] − . 27 Motivated by this successful example, we adopted a similar strategy with Ag NCs. In this work, PPh 3 ligands have been introduced into the NCs successfully together with a dopant.…”