Instituto de Ciencia Molecular (ICMOL), Universitat de València, Paterna 46980, València (Spain).
Department of Chemistry, Texas A&M University, College Station, TX 77842-3012 (USA).
Angew Chem Int Ed Engl. 2015 May 26;54(22):6521-5. doi: 10.1002/anie.201501691. Epub 2015 Apr 14.
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 }⋅45 H2 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 }⋅56 H2 O (2) and Ni2 (II) {Ni(II) 4 [Cu(II) 2 (Me3 mpba)2 ]3 }⋅ 54 H2 O (3). This unique postsynthetic metal substitution affords materials with higher structural stability leading to enhanced gas sorption and magnetic properties.
在化学式为 Mg(II)2{Mg(II)4[Cu(II)2(Me3mpba)2]3}·45H2O（1；Me3mpba(4-)=N,N'-2,4,6-三甲基-1,3-亚苯基双(氧代乙酸盐)）的三维（3D）金属有机骨架（MOF）中，发生了从单晶到单晶的转金属过程。在配位网络内的 Mg(II)离子和通道内的 Mg(II)离子完全被 Co(II)或 Ni(II)离子取代后，1 被转金属化生成化学式为 Co2(II){Co(II)4[Cu(II)2(Me3mpba)2]3}·56H2O（2）和 Ni2(II){Ni(II)4[Cu(II)2(Me3mpba)2]3}·54H2O（3）的两种新型 MOF。这种独特的后合成金属取代赋予了材料更高的结构稳定性，从而提高了气体吸附和磁性性能。
