MOFs are generated from the association of metallic clusters connected by organic linkers toform crystalline porous materials. Their discovery was a breakthrough in the domain ofseparation and gas storage. Unfortunately, MOFs have a low stability and moderate acidityand cannot compete with zeolites for use in industrial catalysis. To design a viable MOFcatalyst, we can take advantage of its almost infinite possibility of customisation. Indeed, alarge choice of metal, linkers or post synthetic modifications allow the creation ofenvironments similar to the active sites of enzymes and can lead to the synthesis of solidswith analogue flexibility or “molecular recognition” properties. This work takes inspirationfrom enzymes to mimic their ability to catalyse reactions with high chemio-, region- andenantio-selectivity in mild conditions. We developed a method for the encapsulation oforganometallic complexes in the large pore of MOF MIL-101. The selectivity of an oxidationreaction was modified and the catalyst was stabilised within the MOF. In addition, four aminofunctionalized MOFs were synthesized as starting materials for post functionalization. Theirflexibility and the active site distribution were controlled by the use of a “mixed linker”strategy: functionalized linkers were diluted with unfunctionalized ones during the synthesis.Lastly, these amino-MOFs were post-functionalized in two steps in isocyanate in order toameliorate the structure reactivity and allow for the grafting of a large range of amines. Thiswork brings the tools for the synthesis of potential “artificial enzymes”.
