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Generalized synthesis of zeolite-type metal-organic frameworks encapsulating immobilized transition-metal clusters.

Zeolites are generally made from tetrahedral nodes and ditopic linkers. Reported here is a versatile method based on trifunctional ligands. With this method, two functional groups are used to form zeolitic nets, while the third one serves to immobilize metal clusters within the channels. The process is driven by the coexistence of multiple inorganic building blocks generated in the heterometallic system. The generality of this method is shown by three distinct metal-organic frameworks mimicking AlPO(4)-5 (AFI) and BCT zeotypes as well as the cubic lcs topology. The correlation between the framework topology and trapped metal species reveals the unique bidirectional control (framework topology ↔ confined metal species) that may be exploited to create a large family of zeotypes with channels modified by different metal ions and clusters.