Intercluster Reactions Resulting in Silver-Rich Trimetallic Nanoclusters

Abstract

Herein, we present an intercluster reaction leading to new trimetallic nanoclusters (NCs) using bimetallic and monometallic NCs as reactants. Dithiol protected bimetallic MAg 28 (BDT) 12 (PPh 3 ) 4 (BDT = 1,3-benzenedithiol and M = Ni, Pd, or Pt) and monothiol protected Au 25 (PET) 18 (PET = 2-phenylethanethiol) were used as model NCs. A mixture of trimetallic MAu x Ag 28−x (BDT) 12 (PPh 3 ) 4 (x = 1− 12) and bimetallic Ag x Au 25−x (PET) 18 (x = 1−7) NCs were formed during the reaction as understood from timedependent electrospray ionization mass spectrometry (ESI MS). Detailed studies of intercluster reaction between Ag 29 (BDT) 12 (PPh 3 ) 4 and Au 25 (PET) 18 were also performed. Although both MAg 28 (BDT) 12 (PPh 3 ) 4 (M = Ag, Ni, Pd, or Pt) and Au 25 (PET) 18 contain 13 atoms icosahedral core, only a maximum of 12 Au doped NCs were formed for the former as a major product and not the 13 Au doped one, unlike the previous reports of intercluster reaction. The transfer of Ni, Pd, or Pt atom from the center of icosahedron of MAg 28 (BDT) 12 (PPh 3 ) 4 to Au 25 (PET) 18 was not observed, which suggests that the central atom is not involved in the reaction. Density functional theory (DFT) calculations were performed to know structures and properties of the formed NCs. This study demonstrates the use of intercluster reaction as an effective synthetic protocol to make multimetallic alloy NCs.

Atomically Precise Alloy Nanoclusters

“…[213,214] Conversely, spectraw ere red shiftedi nt he case of Pd substitution, and the red shiftw as even more pronounced in the case of Ni substitution. [216] These phenomena are very similar to those observed for [Ag 4 M 2 (SR) 8 ] 0 and Ag 25Àx M x (SR) 18 . The absorption peaks in Figures 46 Fa nd Ga re blue shifted from those in Figure 46 A.…”

“…Comparing the spectra in Figures 46 A–D reveals that the absorption peak of [Ag 29 (PPh 3 ) 4 (BDT) 12 ] 3− is blue shifted after Au and Pt substitutions [213, 214] . Conversely, spectra were red shifted in the case of Pd substitution, and the red shift was even more pronounced in the case of Ni substitution [216] . These phenomena are very similar to those observed for [Ag 4 M 2 (SR) 8 ] 0 and Ag 25− x M x (SR) 18 .…”

“…[214] Zhu and co-workerss ynthesized [Ag 17 Cu 12 (PPh 3 ) 4 (BDT) 12 ] 3À and [Ag 16 AuCu 12 (PPh 3 ) 4 (BDT) 12 ] 3À in 2019. [215] In addition, although their geometrical structures have not been determined yet, recently Pradeep et al [216] [213] [Ag 28 Pt(PPh 3 ) 4 (BDT) 12 ] 4À , [214] [Ag 17 Cu 12 (PPh 3 ) 4 (BDT) 12 ] 3À , [215] and [Ag 16 AuCu 12 (PPh 3 ) 4 (BDT) 12 ] 3À , respectively. [215] These NCs have af ramework structure similar to that of [ (x = 2-13); [62] (B) [Au 24 Ag(PPh 3 ) 10 (PET) 5 Cl 2 ] 2 + ; [103] (C) [Au 23 Ag 2 (PPh 3 ) 10 (PET) 5 Cl 2 ] 2 + ; [103] (D) [Au 25Àx Cu x (PPh 3 ) 10 (PET) 5 Cl 2 ] 2 + (x =~3.77); [211] and (E) [Au 24 Pd(PPh 3 ) 10 (PET) 5 Cl 2 ] + .…”

“… Optical absorption spectra of (A) [Ag 29 (PPh 3 ) 4 (BDT) 12 ] 3− , [213] (B) [Ag 29− x Au x (PPh 3 ) 4 (BDT) 12 ] 3− (40 % Au), [213] (C) [Ag 28 Pt(PPh 3 ) 4 (BDT) 12 ] 4− , [213] (D) [Ag 28 Pd(PPh 3 ) 4 (BDT) 12 ] 4− , [216] (E) [Ag 28 Ni(PPh 3 ) 4 (BDT) 12 ] 4− , [216] (F) [Ag 17 Cu 12 (PPh 3 ) 4 (BDT) 12 ] 3− , [215] (G) [Ag 16 AuCu 12 (PPh 3 ) 4 (BDT) 12 ] 3− , [216] (H) [Ag 28 Pt(PPh 3 ) 4 (S‐Adm) 18 ] 2+ , [217] (I) [Ag 28 Pd(PPh 3 ) 4 (S‐Adm) 18 ] 2+ , [219] and (J) [Ag 28 Pt(PPh 3 ) 4 (SC 6 H 11 ) 18 ] 2+ [218] . In (A) and (B), PL spectra are also shown.…”

“…Zhu and co‐workers synthesized [Ag 17 Cu 12 (PPh 3 ) 4 (BDT) 12 ] 3− and [Ag 16 AuCu 12 (PPh 3 ) 4 (BDT) 12 ] 3− in 2019 [215] . In addition, although their geometrical structures have not been determined yet, recently Pradeep et al [216] . have synthesized many novel binary and ternary alloy NCs such as [Ag 28 Pd(PPh 3 ) 4 (BDT) 12 ] 4− , [Ag 28 Ni(PPh 3 ) 4 (BDT) 12 ] 4− , [Ag 28− x Au x Pt(PPh 3 ) 4 (BDT) 12 ] 4− , [Ag 28− x Au x Pd(PPh 3 ) 4 (BDT) 12 ] 4− , and [Ag 28− x Au x Ni(PPh 3 ) 4 (BDT) 12 ] 4− .…”