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Based on the interplay of theory and experiment, a large new family of filledgroup 9 (Co, Rh and Ir) skutterudites is designed and synthesized. The newmaterials fill the empty cages in the structures of the known binary CoSb3,RhSb3 and IrSb3 skutterudites with alkaline, alkaline earth, and rare earthatoms to create compounds of the type AyB4X12; A atoms fill the cages to afraction y, B are the group 9 transition metals, and X is a mixture ofelectronegative main group elements chosen to achieve chemical stability byadjusting the electron counts to electron-precise values. Forty-three newcompounds are reported, antimony-tin and phosphorous-silicon based, with 63compositional variations presented. The new family of compounds is large andgeneral. The results described here can be extended to the synthesis ofhundreds of new group 9 filled skutterudites.

A large new family of filled skutterudites stabilized by electron count