Postsynthetic Ligand and Cation Exchange in Robust Metal–Organic Frameworks

Postsynthetic ligand and metal ion exchange (PSE) processes are shown to readily occur in several "inert" metal-organic frameworks (MOFs), including zeolitic imidazolate frameworks (ZIFs). Ligand exchange can occur between solid samples, as was demonstrated under relatively mild conditions with two robust, topologically distinct MOFs, MIL-53(Al) and MIL-68(In). Interestingly, ligand PSE is not observed with MIL-101(Cr), which is attributed to the kinetic inertness of the Cr(III) ion. In addition to ligand exchange, metal ion (cation) PSE was also studied between intact MOF microcrystalline particles. Metal ion transfer between MIL-53(Al) and MIL-53(Fe) was readily observed. These PSE reactions were monitored and the products characterized by a number of techniques, including aerosol time-of-flight mass spectrometry, which permits single-particle compositional analysis. To show the potential synthetic utility of this approach, the PSE process was used to prepare the first Ti(IV) analogue of the robust UiO-66(Zr) framework. Finally, experiments to rule out mechanisms other than PSE (i.e., aggregation, dissolution/recrystallization) were performed. The results demonstrate that PSE, of either ligands or cations, is common even with highly robust MOFs such as UiO-66(Zr), MILs, and ZIFs. Furthermore, it is shown that PSE is useful in preparing novel materials that cannot be obtained via other synthetic methods.