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Rationalizing and functionalizing stannaspherene: Very stable stannaspherene "alloys".

Aristides D Zdetsis¹

¹Department of Physics, University of Patras, GR-26500 Patras, Greece. zdetsis@upatras.gr

The Journal of Chemical Physics

|December 17, 2009

Summary

The stability of the icosahedral tin dianion (stannaspherene) arises from ionization resistance, not cohesion. This study explores its functionalization and predicts stable, symmetrical tin-bismuth clusters and embedded metal clusters with potential applications.

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Area of Science:

Inorganic Chemistry
Computational Chemistry
Materials Science

Background:

The icosahedral Sn(12)(2-) dianion, or stannaspherene, exhibits high stability.
Isolobal analogy with boranes (B(12)H(12))(2-) provides a framework for understanding and functionalizing tin clusters.
The "boron connection" highlights similarities between group 14 clusters and boron-based compounds.

Purpose of the Study:

To investigate the origin of stannaspherene's stability.
To explore the potential for functionalizing stannaspherene using isolobal analogies.
To predict and theoretically verify the stability and properties of novel tin-containing clusters and their embedded analogs.

Main Methods:

Ab initio calculations
Density Functional Theory (DFT)
High-level computational methods

Main Results:

Stannaspherene's stability is linked to ionization resistance and fluxional rearrangements.
Isovalent Bi(2)Sn(10) and Sb(2)Sn(10) clusters are predicted to be highly stable, symmetrical, and isolobal to Sn(12)(2-).
Embedded clusters M@Sn(12)(2-) and M@Bi(2)Sn(10) (M=Pt, Pd) show high stability, symmetry, large HOMO-LUMO gaps, and significant embedding energies.
Pt@Sn(12)(2-) and Pt@Bi(2)Sn(10) are predicted to be synthesizable.

Conclusions:

The isolobal analogy is a powerful tool for rationalizing and functionalizing group 14 clusters, particularly tin, due to the "inert pair effect".
Novel tin-bismuth clusters and their embedded metal complexes exhibit promising stability and structural properties.
The findings suggest potential for synthesizing new materials with applications analogous to metaloboranes and metalocarboranes.