Flexible Zirconium MOFs as Bromine‐Nanocontainers for Bromination Reactions under Ambient Conditions

A series of flexible MOFs (PCN‐605, PCN‐606, and PCN‐700) are synthesized and applied to reversible bromine encapsulation and release. The chemical stability of these Zr‐MOFs ensures the framework's integrity during the bromine adsorption, while the framework's flexibility allows for structural adaptation upon bromine uptake to afford stronger host–guest interactions and therefore higher bromine adsorption capacities. The flexible MOFs act as bromine‐nanocontainers which elongate the storage time of volatile halides under ambient conditions. Furthermore, the bromine pre‐adsorbed flexible MOFs can be used as generic bromine sources for bromination reactions giving improved yields and selectivities under ambient conditions when compared with liquid bromine. Bromine that's better than bromine: A series of flexible Zr‐based metal–organic frameworks (MOFs) are prepared using a topology guided strategy. During desolvation and bromine adsorption these MOFs undergo significant structural transformations. The bromine pre‐adsorbed flexible MOFs are used as generic bromine sources for bromination reactions giving improved yields and selectivities compared to liquid bromine.