Generic Postfunctionalization Route from Amino-Derived Metal-Organic Frameworks

This study deals with the development of a soft, generic, one-pot postfunctionalization method for metal-organic frameworks (MOFs) starting from compounds with an amino group on the linker. The first step consists of transforming the amino group into azide (N-3) by an unconventional route using tBuONO and TMSN3. In the same vessel, the desired functionalized MOF then is obtained by the Huisgen 1,3-dipolar cycloaddition of azides to alkynes, otherwise known as the click reaction. The method was applied to DMOF-NH2 and MIL-68(In)-NH2, which represent two distinct and important classes of MOF. For both, the functionalization was complete (>90% grafting) and the crystallinity was maintained. Thanks to the large diversity and availability of cyano- and acetylene-based chemicals, this method opens the door to tailor-made functionalized MOFs.