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 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 [NBu(4)](3)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)(BDC)(2)].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.
Rodriguez-Albelo
L Marleny
LM
Zeolite Engineering Laboratory, Institute of Materials Research and Engineering (IMRE), University of Havana, Havana 10400, Cuba.
Ruiz-Salvador
A Rabdel
AR
Sampieri
Alvaro
A
Lewis
Dewi W
DW
Gómez
Ariel
A
Nohra
Brigitte
B
Mialane
Pierre
P
Marrot
Jérôme
J
Sécheresse
Francis
F
Mellot-Draznieks
Caroline
C
Ngo Biboum
Rosa
R
Keita
Bineta
B
Nadjo
Louis
L
Dolbecq
Anne
A