Understanding of multimetallic cluster growth

Area of Science:

• Inorganic Chemistry
• Materials Science
• Computational Chemistry

Background:

• Formation mechanisms of ligand-free inorganic molecules are poorly understood.
• This knowledge gap hinders the planning of synthetic routes for these compounds.
• High coordination flexibility of atoms complicates the identification of reaction intermediates.

Purpose of the Study:

• To investigate the stepwise formation mechanisms of multimetallic clusters.
• To provide a detailed understanding of ligand-free inorganic species synthesis.
• To generalize findings for a broader family of multimetallic clusters.

Main Methods:

• Experimental analysis using a series of crystal structures.
• Complementary quantum-chemical studies.
• Efficient quantum-chemical tools for energy hypersurface screening.

Main Results:

• Detailed elucidation of the stepwise formation of various multimetallic clusters, including (Ge2As2)(2-), (Ge7As2)(2-), [Ta@Ge6As4](3-), [Ta@Ge8As4](3-), and [Ta@Ge8As6](3-).
• First detailed energy hypersurface screening for ligand-free inorganic species formation.
• Semi-quantitative picture of the reaction pathway.

Conclusions:

• The study provides unprecedented insights into the formation mechanisms of ligand-free multimetallic clusters.
• The employed computational methods enable efficient screening of reaction pathways.
• The findings are generalizable to a wider class of related inorganic clusters.