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Issue 20, 2011
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Anion-tuned sorption and catalytic properties of a soft metal–organic solid with polycatenated frameworks

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Abstract

A structurally flexible porous metal–organic framework, [CuII(bped)2(H2O)2(SiF6)] ⊃ 4H2O (Cu-MOF-SiF6) was prepared from CuSiF6 and meso-1,2-bis(4-pyridyl)-1,2-ethanediol (bped) in EtOHH2O. Cu-MOF-SiF6 is a three-dimensional (3D) polycatenated framework consisting of two-dimensional (2D) (4,4) topological grid networks which display 2-fold inclined interpenetration in the crystal lattice. The SiF62 anions hosted in the one-dimensional channels of Cu-MOF-SiF6 can be readily exchanged with NO3 anions while keeping the framework intact, leading to isomorphous Cu-MOF-NO3. The Cu-MOFs show selective adsorption behaviors due to the host–guest interaction, which is dependent on the anions and the guest size. The MeOH uptake investigation indicates that Cu-MOF-SiF6 demonstrates a breathing effect, while Cu-MOF-NO3 exhibits distinctive stepwise MeOH sorption due to the smaller size of NO3 and the larger voids in the crystal lattice. Cu-MOF-NO3 also exhibits stepwise sorption for larger EtOH guests, while the uptake of EtOH is blocked in Cu-MOF-SiF6. In addition, the solids show anion-responsive catalytic properties. Both Cu-MOF-SiF6 and Cu-MOF-NO3 efficiently oxidize benzylic compounds to the corresponding carbonyl functionality under mild and convenient reaction conditions, but improved catalytic activity was observed for Cu-MOF-NO3. The catalysts can be reused with the framework left intact at least three times without losing of any activity.

Graphical abstract: Anion-tuned sorption and catalytic properties of a soft metal–organic solid with polycatenated frameworks

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Publication details

The article was received on 25 Jan 2011, accepted on 04 Mar 2011 and first published on 31 Mar 2011


Article type: Paper
DOI: 10.1039/C1JM10394F
Citation: J. Mater. Chem., 2011,21, 7098-7104
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    Anion-tuned sorption and catalytic properties of a soft metal–organic solid with polycatenated frameworks

    S. Wang, L. Li, J. Zhang, X. Yuan and C. Su, J. Mater. Chem., 2011, 21, 7098
    DOI: 10.1039/C1JM10394F

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