Heterogenization of Trinuclear Palladium Complex into an Anionic Metal–Organic Framework through Postsynthetic Cation Exchange

The innate modular nature of metal–organic frameworks (MOFs) enables postsynthetic modification of the crystalline framework, thereby resulting in novel properties. Anionic MOFs are an interesting category of frameworks since their pore environment can be modified using a simple ion-exchange process. In this work, we demonstrate that via directly ion exchanging an anionic metal–organic framework can not only be the host for a palladium trinuclear transition metal complex but also gain catalytic capability as a hybrid system in the semireduction of internal alkynes. The confined pore space within the MOF structure and the thiol groups of the cluster successfully minimize the detrimental aggregation of palladium during the catalytic process, thereby resulting in a heterogeneous recyclable catalyst system.