Solvothermal synthesis of Group 13–15 chalcogenidometalates with chelating organic amines

Inorganic–organic hybrid chalcogenidometalate materials have attracted considerable interest, because they are a new type of materials with unique topologic structures. The syntheses of these materials are typically carried out under hydro(solvo)thermal conditions at relatively low temperatures. Organic amines have been demonstrated to be successful and versatile molecules to be used in template-directed synthesis of numerous chalcogenide-based open-framework materials. Some comprehensive reviews have summarized the preparation and structures of the chalcogenidometalates with non-chelating amines. Extended and embedded researches on the chelating amines containing a different number of N-donor atoms have recently attracted more interest in synthetic chemistry. A series of unique inorganic–organic hybrid chalcogenidometalate materials are successfully isolated lately. This review focuses on the recent developments in solvothermal synthesis of main group chalcogenidometalates in the presence of organic chelating amines or polyamines as reaction medium. In contrast to the non-chelating amines, the roles of the chelating amines in the syntheses and the effects of the chelating amines on the crystal structures are discussed. A comprehensive outline of the chalcogenidometalate compounds with metal complex cations is also presented.