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Solid State Chemistry of Clathrate Phases: Crystal Structure, Chemical Bonding and Preparation Routes

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Baitinger,  Michael
Michael Baitinger, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Böhme,  Bodo
Bodo Böhme, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Ormeci,  Alim
Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Grin,  Yuri
Juri Grin, Chemical Metal Science, Max Planck Institute for Chemical Physics of Solids, Max Planck Society;

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Citation

Baitinger, M., Böhme, B., Ormeci, A., & Grin, Y. (2014). Solid State Chemistry of Clathrate Phases: Crystal Structure, Chemical Bonding and Preparation Routes. In Physics and chemistry of inorganic clathrates (pp. 35-64). Springer.


Cite as: https://hdl.handle.net/11858/00-001M-0000-0028-F230-9
Abstract
Clathrates represent a family of inorganic materials called cage compounds. The key feature of their crystal structures is a three-dimensional (host) framework bearing large cavities (cages) with 20-28 vertices. These polyhedral cages bear-as a rule-guest species. Depending on the formal charge of the framework, clathrates are grouped in anionic, cationic and neutral. While the bonding in the framework is of (polar) covalent nature, the guest-host interaction can be ionic, covalent or even van-der Waals, depending on the chemical composition of the clathrates. The chemical composition and structural features of the cationic clathrates can be described by the enhanced Zintl concept, whereas the composition of the anionic clathrates deviates often from the Zintl counts, indicating additional atomic interactions in comparison with the ionic-covalent Zintl model. These interactions can be visualized and studied by applying modern quantum chemical approaches such as electron localizability.