Core Charge Density Dominated Size-Conversion from Au₆ P₈ to Au₈ P₈ Cl₂

Area of Science:

• Inorganic Chemistry
• Materials Science
• Computational Chemistry

Background:

• Metal nanoclusters exhibit crucial stimulus-response properties for applications in catalysis and biomedical fields.
• The mechanistic origins of metal nanocluster transformations, particularly size-conversion, remain underexplored.

Purpose of the Study:

• To theoretically investigate the mechanism of size-conversion in gold nanoclusters induced by Au^IPPh₃Cl.
• To elucidate the optimal pathway and key structural parameters governing the growth from [Au₆(DPPP)₄]²⁺ to [Au₈(DPPP)₄Cl₂]²⁺.

Main Methods:

• Density Functional Theory (DFT) calculations were employed to model the size-conversion process.
• Analysis focused on identifying the optimal growth pathway and critical structural parameters.

Main Results:

• The study identified the dissociation of gold-phosphorus (Au-P) bonds as the rate-limiting step in the size-growth mechanism.
• The ease of Au-P bond dissociation was found to be directly correlated with the "core charge density" of the precursor nanocluster.

Conclusions:

• This research provides insights into the structure-reactivity relationships governing metal nanocluster size-conversion.
• The findings contribute to a deeper understanding of the kinetics involved in complex nanocluster systems, benefiting future catalyst and biomedical applications.