Hybrid Assembly of Different-Sized Supertetrahedral Clusters into a Unique Non-Interpenetrated Mn-In-S Open Framework with Large Cavity.

Reported here is a unique crystalline semiconductor open-framework material built from the large-sized supertetrahedral T4 and T5 clusters with the Mn-In-S compositions. The hybrid assembly between T4 and T5 clusters by sharing terminal μ2-S2- is for the first time observed among the cluster-based chalcogenide open frameworks. Such three-dimensional structure displays non-interpenetrated diamond-type topology with extra-large nonframework volume of 82%. Moreover, ion exchange, CO2 adsorption, as well as photoluminescence properties of the title compound are also investigated.