Thermally activated bipyridyl-based Mn-MOFs with Lewis acid-base bifunctional sites for highly efficient catalytic cycloaddition of CO with epoxides and Knoevenagel condensation reactions.

Metal-organic frameworks (MOFs) have become preferred heterogeneous catalytic materials for many reactions due to their advantages such as porosity and abundant active sites. Here, a 3D Mn-MOF-1 [Mn(DPP)(HO)]·6HO (DPP = 2,6-di(2,4-dicarboxyphenyl)-4-(pyridine-4-yl)pyridine) was successfully synthesized under solvothermal conditions. This Mn-MOF-1 possesses a 3D structure constructed by the combination of a 1D chain and the DPP ligand and features a micropore with a 1D drum-like shaped channel. Interestingly, Mn-MOF-1 can maintain the structure unchanged by the removal of coordinated and lattice water molecules, whose activated state (denoted as Mn-MOF-1a) contains rich Lewis acid sites (tetra- and pentacoordinated Mn ions) and Lewis base sites (N atoms). Furthermore, Mn-MOF-1a shows excellent stability, which can be used to catalyze CO cycloaddition reactions efficiently under eco-friendly, solvent-free conditions. In addition, the synergistic effect of Mn-MOF-1a resulted in its promising potential in Knoevenagel condensation under ambient conditions. More importantly, the heterogeneous catalyst Mn-MOF-1a can be recycled and reused without an obvious decrease of activity for at least 5 reaction cycles. This work not only paves the way for the construction of Lewis acid-base bifunctional MOFs based on pyridyl-based polycarboxylate ligands but also demonstrates that Mn-based MOFs hold great promise as a heterogeneous catalyst toward both CO epoxidation and Knoevenagel condensation reactions.