Zeolitic Polyoxometalate-Based Metal−Organic Frameworks (Z-POMOFs): Computational Evaluation of Hypothetical Polymorphs and the Successful Targeted Synthesis of the Redox-Active Z-POMOF1

The targeted design and simulation of a new family of zeolitic metal−organic frameworks (MOFs) based on benzenedicarboxylate (BDC) as the ligand and ε-type Keggin polyoxometalates (POMs) as building units, named here Z-POMOFs, have been performed. A key feature is the use of the analogy between the connectivity of silicon in dense minerals and zeolites with that of the ε-type Keggin POMs capped with Zn(II) ions. Handling the ε-Keggin as a building block, a selection of 21 zeotype structures, together with a series of dense minerals were constructed and their relative stabilities computed. Among these Z-POMOFs, the cristobalite-like structure was predicted to be the most stable structure. This prediction has been experimentally validated by the targeted synthesis of the first experimental Z-POMOF structure, which was strikingly found to possess the cristobalite topology, with three interpenetrated networks. Crystals of [NBu4]3[PMoV8MoVI4O36(OH)4Zn4(BDC)2]·2H2O (Z-POMOF1) have been isolated under hydrothermal conditions from the reduction of ammonium heptamolybdate in the presence of phosphorous acid and Zn(II) ions. Tetrabutylammonium cations play the role of counterions and space-filling agents in this tridimensional interpenetrated framework. Moreover, the electrochemistry of the ε-Keggin POM is maintained and can be exploited in the insoluble Z-POMOF1 framework, as demonstrated by the electrocatalytic reduction of bromate.