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Double Concave Cesium Encapsulation by Two Charged Sumanenyl Bowls
Sarah N Spisak1, Zheng Wei1, Andrey Yu Rogachev2
1Department of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, NY, 12222, USA.
Angewandte Chemie (International Ed. in English)
|February 8, 2017
Summary
Researchers synthesized a novel organometallic sandwich compound featuring cesium encapsulated by two sumanene molecules. This structure showcases unprecedented double concave encapsulation, offering new insights into alkali metal interactions with polycyclic aromatic hydrocarbons.
Area of Science:
- Organometallic Chemistry
- Supramolecular Chemistry
- Materials Science
Background:
- Alkali metals like sodium (Na) and cesium (Cs) exhibit distinct ionic sizes and binding affinities.
- Sumanene (C21H12) is a bowl-shaped polycyclic aromatic hydrocarbon with potential for host-guest chemistry.
- Organometallic sandwich compounds offer unique structural and electronic properties.
Purpose of the Study:
- To investigate the controlled reaction of alkali metals (Na and Cs) with sumanene.
- To synthesize and characterize a novel organometallic sandwich complex.
- To explore the encapsulation of metal ions within sumanene frameworks.
Main Methods:
- Controlled chemical reaction between Na, Cs, and sumanene.
- Crystallization to form a solvent-separated ion pair.
- X-ray crystallography for structural elucidation.
- Computational methods (B2PLYP-D/TZVP/ZORA) for bonding and energetic analysis.
Main Results:
- Successful synthesis of a novel organometallic sandwich complex: [Cs(C21H11-)2]-.
- Crystallographic confirmation of double concave encapsulation of a cesium ion by two sumanenyl anions.
- Formation of a solvent-separated ion pair with a [Na(18-crown-6)(THF)2]+ cation.
- Computational evaluation provided insights into the bonding and energetics of the complex.
Conclusions:
- Demonstrated the formation of an unprecedented organometallic sandwich structure via alkali metal-sumanene interaction.
- Highlighted the unique double concave encapsulation capability of sumanene anions.
- Computational analysis supports the stability and formation mechanism of the synthesized complex.
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