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 intermediate’s 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(NO 3 ) 2 ·6H 2 O, accompanied by a change in morphology from a plate to a cube. Reaction with CuCl 2 ·2H 2 O 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 MnCl 2 . 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.