Enhanced Catalytic Activity of TEMPO-Mediated Aerobic Oxidation of Alcohols via Redox-Active Metal–Organic Framework Nodes

Metal–organic frameworks (MOFs) are outstanding platforms for heterogeneous catalysis due to their tunable pore size, huge surface area, large porosity, and potential active sites. The design and synthesis of MOF/organocatalyst co-catalytic systems have attracted considerable interest owing to their high catalytic activity, low toxicity, and mild reaction conditions. Herein, we reported the synthesis of a bifunctional TEMPO-IsoNTA organocatalyst featuring a pyridyl group as an anchoring site and a TEMPO radical as a catalytic active site. By using the topologically isomorphic structures of MIL-101(Fe) and MIL-101(Cr) as co-catalysts, these MOF/TEMPO-IsoNTA systems enable the efficient aerobic oxidation of various alcohols to their corresponding aldehydes or ketones under mild conditions. Notably, the MIL-101(Fe)/TEMPO-IsoNTA system exhibits superior catalytic activity, thanks to their redox-active FeIII-oxo nodes, which facilitate the regeneration of TEMPO-IsoNTA. Our research not only solves the problem of potential heavy metal contamination in the TEMPO-based homogeneous catalytic system, but also enriches the understanding of synergism of MOFs/organocatalysts.