Disulfide-Driven Pore Functionalization of Metal-Organic Frameworks

Post-synthetic modification (PSM) imparts additional functionality to metal-organic frameworks (MOFs) that is often difficult to access using solvothermal synthesis. As such, expanding the repertory of PSM reactions available to the practitioner is of increased importance for the generation of materials tailored for desired applications. Herein, a method is described for the protecting group-free installation of diverse functional groups within the pores of a MIL-53(Al) analogue via disulfide bond formation. The majority of the reactions proceed with thiol-to-disulfide conversions ranging from high to nearly quantitative. The disulfide bonds are stable in various solvents and can be cleaved in the presence of a reducing agent. A new post-synthetic modification strategy for metal-organic frameworks is presented. Diverse functional groups are installed within an analogue of MIL-53(Al) via disulfide bonds.image