Stable Supersupertetrahedron with Infinite Order via the Assembly of Supertetrahedral T4 Zinc-Indium Sulfide Clusters.

A new family member of T p, q-based hierarchical chalcogenide architecture was created by assembling regular T4-ZnInS clusters into a periodically "hollowed-out" cubic ZnS-type structure framework (T4,∞) via the cross-linker of the tetracoordinated corner μ4-S2-. Ion-exchange and CO2 adsorption experiments suggest that such a structure with a corner μ4-S2- linker has structural stability superior to those of previously reported chalcogenide open frameworks composed of the same T4-ZnInS clusters with a bicoordinated (μ2-S2-) or a tricoordinated (μ3-S2-) cross-linker. Importantly, this case further demonstrates the feasibility of systematically engineering stable porous crystalline chalcogenide frameworks by a "hollow-out" strategy.