Isolation and Chemical Transformations Involving a Reactive Intermediate of MOF-5

We report the isolation of a nonporous plate-like intermediate species (MOF-i) obtained during the synthesis of MOF-5 and the testing of this intermediates reactivity toward three metal ions (Zn^II, Cu^II, and Mn^II) in N,N-dimethylformamide at 120 °C. We obtained interpenetrated MOF-5 crystals from the reaction between MOF-i and Zn(NO₃)₂·6H₂O, accompanied by a change in morphology from a plate to a cube. Reaction with CuCl₂·2H₂O did not disrupt the plate-like morphology of MOF-i, but it did result in the replacement of Zn^II by Cu^II and formation of a novel porous copper MOF. MOF-i showed no reactivity toward MnCl₂. Our results demonstrate that MOF-i imparts a selective reactivity that is different from the individual metal ions employed in conventional synthesis of MOFs and suggests that reactive intermediates may be useful in extending the diversity of metal-organic frameworks.