Thiolate-Protected Trimetallic Au_∼20Ag_∼4Pd and Au_∼20Ag_∼4Pt Alloy Clusters with Controlled Chemical Composition and Metal Positions

Abstract

The mixing of heteroelements in metal clusters is a powerful approach to generate new physical/chemical properties and functions. However, as the kinds of elements increase, control of the chemical composition and geometric structure becomes difficult. We succeeded in the compositionally selective synthesis of phenylethanethiolate-protected trimetallic AuAgPd and AuAgPt clusters, AuAgPd(SCHPh) and AuAgPt(SCHPh). Single-crystal X-ray structural analysis revealed the precise position of each metal element in these metal clusters. Reacting with thiol at an elevated temperature was found to be important to direct the metal elements to the most stable positions. The electronic structures of these trimetallic clusters become more discretized than those of the related bimetallic clusters due to orbital splitting.

Atomically Precise Alloy Nanoclusters

“…[30][31][32][33][34][35][36][37][38][39]41] Similar researchh as recently been undertaken by several groups,a nd their findings have demonstrated that the mixing( alloying) of heteroelements is an extremelye ffective means to modulate the electronic structure and functions of NCs. [66][67][68][69][70][71][72][73][74][75][76][77][78][79][80][81][82][83] In addition,…”

“…Reproduced with permission from references [73], [125],a nd [136][137][138][139][140]. [74,76,105] Reproduced with permission from references [74,76] and [105].Copyright2 018 American Chemical Society, Copyright 2016R oyal SocietyofC hemistry,and Copyright 2015 AmericanC hemical Society. the centera nd surface of the metal core (Figure 13 A).…”

“…For example, Negishi and colleagues selectively synthesized [Au~2 0 Ag~4M(PET) 18 ] 0 (M = Pt or Pd) containing Pt and Ag or Pd and Ag as heteroelements (Figure 14 B). [74] In addition, syntheses and determination of the geometrical structures of trimetallic [Au 24Àx Ag x Hg(PET) 18 ] 0 (x = 0-3), [Au 24Àx Ag x Hg(PET) 18 ] 0 (x = 5-8), and [Au 24Àx Ag x Cd(PET) 18 ] 0 (x = 2-6) have been reported. [150,151] The synthesis of [Au 24ÀxÀy Ag x Cu y Pd(SR) 18 ] 0 NCsc ontaining four types of metals has also been achieved, although their geometrical structure has not been determined (Figure 14 C).…”

One-, Two-, and Three-Dimensional Self-Assembly of Atomically Precise Metal Nanoclusters

“…Therefore, if the number of constituent atoms of metal NCs is controlled, it is possible to produce various physical/chemical properties and functions by using only one type of metal element. If several types of elements can be used, it becomes possible to obtain more functionalities [ 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 , 75 , 76 , 77 , 78 , 79 , 80 , 81 , 82 ]. For these reasons, metal NCs have been attracting considerable attention as a central material in nanotechnology.…”

Intramolecular Metal Exchange Reaction Promoted by Thiol Ligands

“…More importantly, the metal exchange process can jump out of the metal activity sequence, which provides a new way to synthesize the gold nanocluster with a highly active metal (e.g., Cd) [8,9]. So far, two types of metal exchange reactions have been reported: (i) Metal exchange with metal complexes [10,11,12,13,14,15]. This reaction can be created between thiolated metal complexes (e.g., Ag(SR)) and thiolated gold nanoclusters.…”