Alloying dichalcogenolate-protected Ag₂₁ eight-electron nanoclusters: a DFT investigation

Area of Science:

• Inorganic Chemistry
• Computational Chemistry
• Materials Science

Background:

• Dichalcogenolato nanoclusters with the formula [Ag21{E2P(OR)2}12]+ (E = S, Se) possess a core M@M12 icosahedral structure.
• These nanoclusters are amenable to isoelectronic doping with various heteroatoms.

Purpose of the Study:

• To systematically investigate the effects of isoelectronic doping on silver nanoclusters using Density Functional Theory (DFT) calculations.
• To understand heteroatom site occupation preferences within the nanocluster structure.
• To explore the impact of doping on the optical properties of these complexes.

Main Methods:

• Density Functional Theory (DFT) calculations were employed to model the electronic structure and stability of doped nanoclusters.
• Trends in heteroatom site occupation were analyzed across groups 9-12.
• Time-Dependent DFT (TD-DFT) calculations were used to assess changes in optical properties.

Main Results:

• All investigated doped nanoclusters maintained the M@M12 icosahedral core, with minor energy differences between structural variations.
• Three distinct alloying sites (central, icosahedral, peripheral) were identified, and site occupation preferences were determined for heteroatoms across groups 9-12.
• Experimental results corroborated the predicted trends in site occupation.
• Rationalization of trends was based on electronegativity, d-orbital involvement in bonding, and atomic size.

Conclusions:

• Heteroatom doping significantly influences the electronic and optical properties of [Ag21{E2P(OR)2}12]+ nanoclusters.
• The study provides a framework for understanding and predicting doping behavior based on fundamental atomic and electronic properties.
• The findings are expected to drive further research into tuning luminescence properties of dithiolato and diseleno silver nanoclusters.