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An efficient multi-gram access in a two-step synthesis to soluble, nine-atomic, silylated silicon clusters
Kevin M Frankiewicz1,2, Nicole S Willeit1,2, Viktor Hlukhyy1
1Department of Chemistry, TUM School of Natural Sciences, Technical University of Munich (TUM), Lichtenbergstraße 4, D-85748, Garching, Germany.
Nature Communications
|December 23, 2024
Summary
Researchers developed a simple method to synthesize soluble silicon-9 (Si9) clusters. This breakthrough simplifies the production of silicon-rich molecules, paving the way for new advancements in silicon Zintl chemistry.
Area of Science:
- Inorganic Chemistry
- Materials Science
- Solid-State Chemistry
Background:
- Silicon is a crucial semiconducting material, but synthesizing silicon-rich molecules in solution is challenging.
- Existing multi-step syntheses for unsaturated silicon-rich molecules are often inefficient.
Purpose of the Study:
- To develop a straightforward synthetic route to soluble, polyhedral silicon-9 (Si9) clusters.
- To overcome challenges posed by reactive [Si4]4- ions in the K12Si17 precursor phase.
Main Methods:
- Fractional crystallization was employed to separate interfering [Si4]4- ions from the K12Si17 phase.
- Isolation of Si9 clusters as monoprotonated [Si9H]3- ions.
- Crystallization of the product as a 2.2.2-Cryptate salt.
Main Results:
- A two-step procedure yields multi-gram quantities (20 grams) of soluble Si9 clusters.
- Successfully isolated monoprotonated [Si9H]3- ions, overcoming the reactivity of [Si4]4-.
- Demonstrated the utility of the product for further silicon Zintl chemistry, including the synthesis of a trisilylated cluster.
Conclusions:
- This work provides a new, efficient starting point for silicon Zintl chemistry.
- The straightforward access to Si9 clusters enables further structural characterization and exploration of silicon cluster chemistry.
