Synthesis, structural characterization and selectively catalytic properties of metal–organic frameworks with nano-sized channels: A modular design strategy

Modular design method for designing and synthesizing microporous metal–organic frameworks (MOFs) with selective catalytical activity was described. MOFs with both nano-sized channels and potential catalytic activities could be obtained through self-assembly of a framework unit and a catalyst unit. By selecting hexaaquo metal complexes and the ligand BTC (BTC=1,3,5-benzenetricarboxylate) as framework-building blocks and using the metal complex [M(phen)2(H2O)2]2+ (phen=1,10-phenanthroline) as a catalyst unit, a series of supramolecular MOFs 1–7 with three-dimensional nano-sized channels, i.e. [M1(H2O)6]·[M2(phen)2(H2O)2]2·2(BTC)·xH2O (M1, M2double bond; length as m-dashCo(II), Ni(II), Cu(II), Zn(II), or Mn(II), phen=1,10-phenanthroline, BTC=1,3,5-benzenetricarboxylate, x=22−24), were synthesized through self-assembly, and their structures were characterized by IR, elemental analysis, and single-crystal X-ray diffraction. These supramolecular microporous MOFs showed significant size and shape selectivity in the catalyzed oxidation of phenols, which is due to catalytic reactions taking place in the channels of the framework. Design strategy, synthesis, and self-assembly mechanism for the construction of these porous MOFs were discussed.