Templated Assembly of Sulfide Nanoclusters into Cubic-C₃N₄ Type Framework

Here we report a new type of nanocluster superlattice in which each four-connected cluster ([M4In16S31],- M = Fe, Co, Zn, and Cd) alternates with a three-connected sulfur anion (S2-) to form a rare and yet theoretically important non-centrosymmetric and non-interpenetrating (3,4)-connected net topologically identical to that of the hypothetical cubic carbon nitride type net. These materials have a ring size consisting of 16 tetrahedral atoms. Because of the large cluster size and the elimination of structural intergrowth, the volume fraction of the inorganic framework is as low as 38%. A strong photoluminescent emission has also been observed.