The Early Development of Inorganic Clathrates

In this chapter the authors relate the discovery of the first inorganic clathrates, Na8Si46 and NaxSi136 (3 ≤ x ≤ 11), whose cage-like structures were determined by comparison with those of the two most classical gas and liquid clathrate hydrates. The main characteristics of clathrate compounds are recalled and a brief review of clathrate hydrates is given. The different polyhedral cages and their arrangements in the so-called type I structure (Na8Si46) and type II structure (NaxSi136) are described in details. The synthesis, composition and structure of other inorganic clathrates of silicon, germanium and tin with potassium, rubidium and cesium as guest atoms are reported. The crystal structure (type I or type II) and corresponding composition is closely related to the size of the guest alkali atoms. The formation of the characteristic polyhedral cages with a majority of pentagonal faces is discussed, and results from the arrangement of all the tetrahedrons in eclipsed position. The relation between clathrate structures and those of clathrasils (silica-based clathrates), Frank-Kasper alloys and fullerene forms of carbon is also discussed. The first measurements of the physical properties of inorganic clathrates are reviewed, including electrical conductivity, thermal properties, high pressure behavior, NMR and ESR investigations. The ability for the silicon, germanium and tin host lattices to form non-stoichiometric and mixed frameworks with elements of neighboring groups is briefly described, giving rise to a large variety of new inorganic clathrates with ionic guest-host interactions and semiconducting properties.