Organometallic catalysts confined inside MOF nanospace

The confinement of organometallic catalyst inside the cavity of porous materials was reported to enhance selectivity and activity [1] Metal-Organic-Framework appear to be appealing platforms for immobilization of organometallic catalyst as already reported by some of us.[2] We present here two methodologies to anchor organometallic species inside a MOF. By Post Synthetic Ligand Exchange (PSLE, see scheme) we achieved the insertion of a Ru-Bipy moiety inside the framework of UIO-67 [Zr6(OH)4(O)4(O2C-C6H4-C6H4-CO2)6], by replacing 10% of the native ligand and used the fully caracterised material as photocatalyst for CO2 reduction. By Post Synthetic Functionalization (PSF, see scheme), we achieved amino acid grafting inside the cavities of Al-MIL-101-NH2 [Al3OCl(O2C-C6H3(NH2)-CO2)3], en route to the creation of chiral materials for asymetric catalysis. Beyond confinement effect, the MOF cavity offers cooperative interactions with metal nodes and/or organic linkers which contribute to he enhanced selectivity.