Highly Robust Metal-Organic Framework for Efficiently Catalyzing Knoevenagel Condensation and the Strecker Reaction...

Metal-organic frameworks (MOFs) have been recognized as one of the most promising porous materials and offer great opportunities for the rational design of new catalytic solids having great structural diversity and functional tunability. Despite numerous inherent merits, their chemical environment instability limits their practical usage and demands further exploration. Herein, by employing the mixed-ligand approach, we have designed and developed a robust 3D Co-MOF, [Co₂(μ₂-O)(TDC)₂(L)(H₂O)₂]·2DMF (H₂TDC = 2,5-thiophenedicarboxylic acid, L = 3,3'-azobispyridine), IITKGP-50 (IITKGP stands for the Indian Institute of Technology Kharagpur), which exhibited excellent framework robustness not only in water but also in a wide range of aqueous pH solutions (pH = 2-12). Taking advantage of superior framework robustness and the presence of high-density open metal sites, IITKGP-50 was further explored in catalyzing the two-component Knoevenagel condensation reaction and three-component Strecker reactions. Moreover, to verify the size selectivity of IITKGP-50, smaller to bulkier substrates in comparison with the MOF's pore cavity (8.1 × 5.6 Ų) were employed, in which relatively lesser conversions for the sterically bulkier aldehyde derivatives confirmed that the catalytic cycle occurs inside the pore cavity. The easy scalability, lower catalyst loading compared to that of benchmark MOFs, magnificent conversion rate over a wide range of substrates, and excellent recyclability without significant performance loss made IITKGP-50 a promising heterogeneous catalyst candidate.