Abstract
Whole series of nanoparticles have now been reported, but probing the competing or coexisting effects in their synthesis and growth remains challenging. Here, we report a bi-nanocluster system comprising two ultra-small, atomically precise nanoclusters, AuAg24(SR)18− and Au2Ag41(SR)26(Dppm)2+ (SR = cyclohexyl mercaptan, Dppm = bis(diphenylphosphino)-methane). The mechanism by which these two nanoclusters coexist is elucidated, and found to entail formation of the unstable AuAg24(SR)18−, followed by its partial conversion to Au2Ag41(SR)26(Dppm)2+ in the presence of di-phosphorus ligands, and an interdependent bi-nanocluster system is established, wherein the two oppositely charged nanoclusters protect each other from decomposition. AuAg24(SR)18 and Au2Ag41(SR)26(Dppm)2 are fully characterized by single crystal X-ray diffraction (SC-XRD) analysis – it is found that their co-crystallization results in single crystals comprising equimolar amounts of each. The findings highlight the interdependent relationship between two individual nanoclusters, which paves the way for new perspectives on nanocluster formation and stability.
Highlights
Whole series of nanoparticles have been reported, but probing the competing or coexisting effects in their synthesis and growth remains challenging
The synthesis of the title nanoclusters was performed in a one-pot method
The stable precursor Ag-Au-Dppm complex was synthesized as a solution in toluene
Summary
Whole series of nanoparticles have been reported, but probing the competing or coexisting effects in their synthesis and growth remains challenging. The size focusing method for synthesizing atomically precise nanoparticles (nanoclusters), wherein the influence of reaction conditions (reaction temperature, growth kinetics, ligand bulkiness, etching time, ligand/metal ratio) on product nanoparticle size distribution are mapped out and adjusted such that a specific size of product nanoparticles are obtained, is quite similar to the concept of “survival of the fittest”[35,36]. The size focusing method does not necessarily result in monodisperse nanoclusters, and is more likely to afford a mixture of several different monodisperse nanoclusters These nanoclusters can be regarded as the “fittest” in the environment in which they were formed, but they can be separated and fully characterized, such studies generally do not inform our understanding of the relationship between them. We report the synthesis and characterization of a binanocluster system, AuAg24 and Au2Ag41, and the interdependent relationship between these two nanoclusters are mapped out. Co-crystallization of AuAg24 and Au2Ag41 resulted in crystals consisting of each of them in a molar ratio of 1:1
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