An alternative pathway for the synthesis of isocyanato- and urea-functionalised metal-organic frameworks.

We have developed a generic two-step post-functionalisation technique for transforming amino-functionalised MOFs into their isocyanate analogues. The first part of the synthetic pathway consists in the conversion of the amino moieties into azido groups. Next, the thermal activation of these azido groups leads to nitrene species that can react with carbon monoxide to yield the desired products. As a proof of concept, this method was applied to the highly stable Al-MIL-53-NH2 and to the acid-sensitive In-MIL-68-NH2. The resulting nitrene species were highly reactive, with side reactions dominating initially. This issue was overcome through the use of a mixed-linker strategy applied during the MOF synthesis that decreased the nitrene radical density within the pore, thereby permitting In-MIL-68-NH2 to be converted into its isocyanate analogue with 100% selectivity. To illustrate the potential of this method for grafting a wide library of potentially active organic groups inside MOFs, amines were condensed onto isocyanato MOFs to form urea analogues.