Isolation of the Secondary Building Unit of a 3D Metal-Organic Framework through Clip-Off Chemistry, and Its Reuse To Synthesize New Frameworks by Dynamic Covalent Chemistry.

Herein, we present a novel methodology for synthesizing metal clusters or secondary building units (SBUs) that are subsequently employed to construct innovative metal-organic frameworks (MOFs) via dynamic covalent chemistry. Our approach entails extraction of SBUs from preformed MOFs through complete disassembly by clip-off chemistry. The initial MOF precursor is designed to incorporate the desired SBU, connected exclusively by cleavable linkers (in this study, with olefinic bonds). Cleavage of all the organic linkers (in this study, via ozonolysis under reductive conditions) liberates the SBUs functionalized with aldehyde groups. Once synthesized, these SBUs can be further reacted with amines in dynamic covalent chemistry to build new, rationally designed MOFs.