Hetero-biicosahedral [Au₂₄Pd(PPh₃)₁₀(SC₂H₄Ph)₅Cl₂]⁺ nanocluster: selective synthesis and optical and electrochemical properties

Abstract

A recent study implied that a hetero-biicosahedral 25-atom cluster composed of two kinds of icosahedral 13-atom clusters could serve as a molecular rectifier and dipole material. However, no hetero-biicosahedral 25-atom clusters containing three types of ligands, in this case, phosphines, halogens, and thiolates, have been reported. In this study, we selectively synthesized [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]Cl (Au = gold, Pd = palladium, PPh3 = triphenylphosphine, SC2H4Ph = phenylethanethiolate, Cl = chloride), in which one Au was replaced with a Pd. The single-crystal X-ray structural analysis demonstrated that [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]Cl was a hetero-biicosahedral 25-atom cluster in which the central atom of one icosahedral Au13 core was replaced by a Pd atom. Optical absorption spectroscopy suggested that the electronic structure of each individual icosahedral 13-atom core in [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ was reasonably well maintained, similar to the case of [Au25(PPh3)10(SC2H4Ph)5Cl2]2+. Density functional theory calculation revealed that the peak splitting in the region below 2.2 eV of the optical absorption spectrum of [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ is due to the splitting of HOMOs and also suggested that this cluster has dipole moment. Electrochemical measurements showed that [Au24Pd(PPh3)10(SC2H4Ph)5Cl2]+ was relatively stable to reduction. These results are expected to contribute to the development of molecular rectifiers and dipole materials based on hetero-biicosahedral 25-atom clusters.

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,…”

“…[211] Negishie tal. [77] synthesized [Au 24 Pd(PPh 3 ) 10 (PET) 5 Cl 2 ] + containing one Pd atom in 2018. [62] (B) [Au 25Àx Ag x (PPh 3 ) 10 (PET) 5 Cl 2 ] 2 + (x = 2-13), [62] (C) [Au 23 Ag 2 (PPh 3 ) 10 (PET) 5 Cl 2 ] 2 + , [103] (D) [Au 24 Cu(PPh 3 ) 10 (PET) 5 Cl 2 ] 2 + , [103] (E) [Au 25Àx Cu x (PPh 3 ) 10 (PET) 5 Cl 2 ] 2 + (x =~3.77), [211] and (F) [Au 24 Pd(PPh 3 ) 10 (PET) 5 Cl 2 ] + .…”

The Ligand‐Exchange Reactions of Rod‐Like Au25‐nMn (M=Au, Ag, Cu, Pd, Pt) Nanoclusters with Cysteine – A Density Functional Theory Study

“…Our group prepared a series of alloy rod‐like Au 25‐n M n nanoclusters, including [Au 12 Ag 13 (PPh 3 ) 10 (SC 2 H 4 Ph) 5 Cl 2 ] 2+ , [Ag 1 Au 24 (PPh 3 ) 10 (SC 2 H 4 Ph) 5 Cl 2 ] 2+ and [Cu 1 Au 24 (PPh 3 ) 10 (SC 2 H 4 Ph) 5 Cl 2 ] 2+ via the metal‐exchange and single foreign atom‐doping strategies . Recently, Negishi and co‐workers prepared the rod‐like [Pd 1 Au 24 (PPh 3 ) 10 (SC 2 H 4 Ph) 5 Cl 2 ] + with size‐focusing method . The structures of all the aforementioned NCs have been well characterized by SCXRD or determined by theoretical calculations.…”

Face‐Centered‐Cubic Ag Nanoclusters: Origins and Consequences of the High Structural Regularity Elucidated by Density Functional Theory Calculations

“…To verify this assumption, we carriedo ut DFT calculations on the A-(B) n -A and B-(A) n -B model NCsa tt he PBE [41,42] /DNP-ECP level of theory.T or educe computational costs, -SMe and PMe 3 were used as model ligandsi na ll clusters, an economy validatedi nr ecent studies. [28,[44][45][46][47][48] The geometry optimization of Ag 38 , Ag 46 , Ag 63 ,a nd Ag 67 startedw ithas implified structure of the reported single-crystal X-ray structures, whereas the startingg eometries of Ag 25 , Ag 88-a ,a nd Ag 88-b were constructed by using theoretical modeling software (according to the aforementioned atomic arrangement rules). The results of these calculations not only verified the proposed frameworks of…”