Ag₂Au₅₀(PET)₃₆ Nanocluster: Dimeric Assembly of Au₂₅(PET)₁₈ Enabled by Silver Atoms

Abstract

The assembly of atomically precise metal nanoclusters offers exciting opportunities to gain fundamental insights into the hierarchical assembly of nanoparticles.H owever,itisstill challenging to control the assembly of individual nanoclusters at amolecular or atomic level. Herein, we report the dimeric assembly of Au 25 (PET) 18 (PET = 2-phenylethanethiol), where two Au 25 (PET) 18 monomers are bridged together by two Ag atoms to form the Ag 2 Au 50 (PET) 36 dimer.T he Ag 2 Au 50 (PET) 36 dimer is au nique mesomer,w hich has not been found in any other chiral metal nanoclusters.F urthermore,t he Ag 2 Au 50 (PET) 36 dimer is distinct from the Au 25-(PET) 18 monomer in its optical, electronic, and catalytic properties.This study is expected to provide afeasible strategy to precisely modulate the assembly of metal nanoclusters with controllable structures and properties.

Molecular reactivity of thiolate-protected noble metal nanoclusters: synthesis, self-assembly, and applications

“…7a), where a single Ag is accommodated in the pocket-like cavity of [Au 25 (S-C 2 H 4 Ph) 18 ] À , forming a Ag-S bond with another NC. 187 In addition to M-S bonds, dimerization and trimerization can also be achieved by introducing dithiolate ligands as crosslinkers. 188 For example, Lahtinen et al carried out a ligand exchange of Au 102 (p-MBA) 44 with bidentate biphenyl-4,4 0dithiols (SH-Ph-Ph-SH), which covalently linked Au 102 NCs into dimers or trimers.…”

Atomically Precise Metal Nanoclusters: Novel Building Blocks for Hierarchical Structures

“…Despite the aforementioned results, the formation of stable, atomically precise dimers is still an open challenge that requires high‐level purification procedures and proper control over the ligand‐bridging strategy, especially to minimize intra‐cluster thiol exchange or the formation of oligomers as side products [58] . An alternative strategy to modulate the assembly of NCs to form atomically precise dimers has been recently described [59] . In their study, Liu et al.…”

“…[58] An alternative strategy to modulate the assembly of NCs to form atomically precise dimers has been recently described. [59] In their study,L iu et al used Ag as the bridge between two NCs to make as table Ag 2 Au 50 (PET) 36 dimer exhibitingi nteresting optical and catalytic properties.…”

Atomically precise structures of Pt2(S-Adam)4(PPh3)2 complexes and catalytic application in propane dehydrogenation

“…3,4 In the recent decades, atomically precise metal nanoclusters, containing a well-defined number of metal atoms and ligands, have aroused an emerging research interest both in fundamental research and functional applications. [5][6][7][8][9][10][11] From nanoparticles to nanoclusters, the physicochemical properties of metals have been changed dras-tically, such as the surface plasmon resonance of nanoparticles becoming the discrete electronic structure of nanoclusters. 12,13 On the other hand, single-atom metal catalysts, atomically dispersed active metal sites on supports, have attracted longstanding attention, owing to their efficient atom utilization and excellent catalytic performance.…”