Postsynthetic Improvement of the Physical Properties in a Metal-Organic Framework through a Single Crystal to Single Crystal Transmetallation.
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abstract
A single crystal to single crystal transmetallation process takes place in the three-dimensional (3D) metal-organic framework (MOF) of formula Mg(II) 2 {Mg(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }45H2 O (1; Me3 mpba(4-) =N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)). After complete replacement of the Mg(II) ions within the coordination network and those hosted in the channels by either Co(II) or Ni(II) ions, 1 is transmetallated to yield two novel MOFs of formulae Co2 (II) {Co(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }56H2 O (2) and Ni2 (II) {Ni(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 } 54H2 O (3). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and magnetic properties.