Framework Adaptability and Concerted Structural Response in a Bismuth Metal‐Organic Framework Catalyst.

Bismuth metal–organic frameworks (MOFs) as heterogeneous catalysts are scarce, and there is little knowledge on the influence of the MOF features on their resulting activity and behavior. Here, we present the synthesis, characterization, and catalytic activity in the one‐pot multicomponent Strecker reaction with ketones of three new MOFs prepared with the combination of indium or bismuth and 4,4′,4′′,4′′′‐methanetetrayltetrabenzoic acid. One of them, denoted BiPF‐7, is very robust and chemically stable, and demonstrates a high activity in the formation of the desired α‐aminonitriles. The interaction of the catalytic substrates with the metal centers in this MOF has been crystallographically characterized, showcasing a concerted framework adaptability process that involves structural changes in framework components that are not directly involved in the binding of the guests.