Dual-fixations of europium cations and TEMPO species on metal-organic frameworks for the aerobic oxidation of alcohols

The efficient and selective aerobic oxidation of alcohols has been investigated with judicious combinations of europium-incorporated and/or TEMPO ((2,2,6,6-tetramethylpiperidin-1-yl)oxyl)-functionalized zirconium-based porous metal-organic frameworks (MOFs). Although MOFs are well-known catalytic platforms for the aerobic oxidation with radical-functionalities and metal nanoparticles, these systematic approaches involving metal cations and/or radical species introduce numerous interesting aspects for cooperation between metals and TEMPO for the aerobic oxidation of alcohols. The role of TEMPO as the oxidant in the heterogeneous catalytic aerobic oxidation of alcohols was revealed through a series of comparisons between metal-anchored, TEMPO-anchored, and metal and TEMPO-anchored MOF catalysis. The fine tunability of the MOF allowed the homogeneously and doubly functionalized catalysts to undergo organic reactions in the heterogeneous media. In addition, the well-defined and carefully designed heterogeneous molecular catalysts displayed reusability along with better catalytic performance than the homogeneous systems using identical coordinating ligands. The role of metal-cation fixation should be carefully revised to control their coordination and maximize their catalytic activity. Lastly, the metal cation-fixed MOF displayed better substrate tolerance and reaction efficiencies than the TEMPO-anchored MOF or mixture MOF systems.