Linker Deprotonation and Structural Evolution on the Pathway to MOF-74.

The synthesis of MOF-74 (MOF = metal-organic framework) proceeds first through the generation of chemically and topologically distinct materials, referred to as phases, displaying exclusively carboxylate coordination, followed by further deprotonation to enable oxo coordination and MOF-74 formation. The synthesis of Mg-MOF-74 at high concentrations of linker and metal enables the stabilization and characterization of the previously unobserved, exclusively carboxylate coordinating phases. Ex situ and in situ approaches are leveraged to provide the time-resolved observation of Mg-MOF-74 synthesis and the formation of phases that precede Mg-MOF-74 formation as well as metastable phase dissolution. These data support dissolution and redeposition as the mechanism of MOF-74 formation and provide insight into the formation mechanism of MOFs with multiple linker coordination types.