Octahedral rhenium(III) chalcocyanide cluster anions: Synthesis, structure, and solid state design

The review summarizes data on synthesis and structure of rhenium chalcocyanide cluster anions [Re6X8(CN)(6)](4-) (X = S, Se, Te) belonging to a new class of inorganic compounds. Two main groups of such compounds are considered: salts with an island structure and polymer compounds. Various factors governing the type of structure and the dimensionality of the polymer compounds are analyzed including the nature of the chalcogen atom in the cluster anion, preferable coordination of the transition metal cation, and the size of additional charge-compensating cations. Crystal-chemical approaches to design of complex salts based on octahedral rhenium chalcocyanide cluster anions are formulated.