Inclusion compounds featuring guest anions trapped in large polyhedral cavities of positively charged frameworks are known as cationic clathrates. They are based on the group 14 elements and form various crystal structures composed of polyhedra that have at least 20 vertices. Together with their counterparts�anionic clathrates�they receive much attention as possible thermoelectric materials for mid- or high-temperature heat-to-power conversion. It is assumed that the spatial separation of host and guest substructures in clathrates facilitates concurrent optimization of the heat and charge carriers' transport, which is a necessary condition for creating a thermoelectric material. This paper focuses on the structure-property relations for the cationic clathrates. Discussed will be the variety of the clathrate crystal structures and superstructures, thermal and chemical stability of the cationic clathrates, their transport properties, and the prospects of optimizing their thermoelectric performance towards new materials.

Chemistry of cationic clathrates: From aesthetically beautiful structures to unconventional thermoelectric materials

244th National Meeting (2012)

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