Pushing up the size limit of chalcogenide supertetrahedral clusters: two- and three-dimensional photoluminescent open frameworks from (Cu(5)In(30)S(54))(13-) clusters.

Direct band gap copper indium chalcogenides are of great technological importance in part because of their high photovoltaic conversion efficiency. Covalent superlattices constructed from copper indium chalcogenide clusters are of particular interest because they may combine open framework architecture with semiconducting properties. Here two photoluminescent covalent superlattices built from core-shell type copper indium sulfide supertetrahedral clusters are reported. Each cluster consists of 35 metal cations and is so far the largest known supertetrahedral cluster with a metal-to-metal distance of 1.6 nm. In addition, this is the first example of supertetrahedral clusters in heterometallic copper indium chalcogenides. The preparation of these large clusters has narrowed down the size gap between colloidal nanoclusters and small supertetrahedral clusters and revealed new possibilities in the construction of nanoporous semiconducting superlattices with tunable pore size. Through the combination of metal ions with different oxidation states to provide both overall and local charge neutrality, an effective approach has been demonstrated in the rational synthesis of chalcogenide open framework materials with large and unprecedented supertetrahedral clusters.