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

Rodriguez-Albelo, LM; Ruiz-Salvador, AR; Sampieri, A; Lewis, DW; Gomez, A; Nohra, B; ... Dolbecq, A; + view all (2009) Zeolitic Polyoxometalate-Based Metal-Organic Frameworks (Z-POMOFs): Computational Evaluation of Hypothetical Polymorphs and the Successful Targeted Synthesis of the Redox-Active Z-POMOF1. J AM CHEM SOC , 131 (44) 16078 - 16087. 10.1021/ja905009e.

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Abstract

The targeted design and simulation of a new family of zeolitic metal-organic frameworks (MOFs) based on benzenedicarboxylate (BDC) as the ligand and epsilon-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 epsilon-type Keggin POMs capped with Zn(II) ions. Handling the epsilon-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)[(PMO8MO4O36)-M-V-O-VI(OH)(4)Zn-4(BDC)(2)]center dot 2H(2)O (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 epsilon-Keggin POM is maintained and can be exploited in the insoluble Z-POMOF1 framework, as demonstrated by the electrocatalytic reduction of bromate.

Type:Article
Title:Zeolitic Polyoxometalate-Based Metal-Organic Frameworks (Z-POMOFs): Computational Evaluation of Hypothetical Polymorphs and the Successful Targeted Synthesis of the Redox-Active Z-POMOF1
DOI:10.1021/ja905009e
Keywords:CARBON-PASTE ELECTRODES, MOLECULAR-DYNAMICS SIMULATIONS, IMIDAZOLATE FRAMEWORKS, COORDINATION POLYMERS, CRYSTAL-STRUCTURE, BUILDING-BLOCKS, GIANT PORES, DESIGN, CHEMISTRY, ELECTROCHEMISTRY
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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