A Robust, Redox-Active Cerium Metal–Organic Framework for the Aerobic Oxidation of Benzylamines to Benzylimines

Heterogeneous catalysis has become a cornerstone of modern sustainable chemistry and green technology, with growing global emphasis on cleaner, more efficient processes. Here, a highly crystalline and redox-active cerium-based metal-organic framework (<b>1</b>) was synthesized using the 2,5-bis(allyloxy)terephthalic acid linker via solvothermal synthesis and thermally activated to obtain <b>1'</b>. Thus, <b>1'</b> was characterized using thermogravimetric analysis, Brunauer-Emmett-Teller, powder X-ray diffraction, field emission scanning electron microscopy, and field emission transmission electron microscopy, revealing its excellent thermal stability and well-defined morphology. The accessible Ce(III)/Ce(IV) centers within the framework of <b>1'</b> facilitated efficient heterogeneous catalysis for the aerobic oxidation of benzylamines to benzylimines. The catalytic performance of <b>1'</b> was investigated for the aerobic oxidation of benzylamine to its respective imine using molecular oxygen as an oxidant. The catalyst exhibited quantitative conversion and high selectivity under neat reaction conditions, highlighting the role of redox-active Ce(III)/Ce(IV) centers and accessible pore channels in enabling efficient substrate activation. Moreover, the catalyst's heterogeneous nature enabled easy recovery and reuse with minimal loss of activity, confirming its stability and recyclability. Overall, the study establishes <b>1'</b> as an efficient, environmentally benign, and reusable catalyst for selective oxidative transformations, offering valuable insights into the design of MOF-based catalytic systems for sustainable organic synthesis.