Control of the Porosity in Manganese Trimer-Based Metal-Organic Frameworks by Linker Functionalization

Manganese complexes have attracted significant interest in chemical industries and academic research for their application as catalysts owing to their ability to attain a variety of oxidation states. Generally, sterically bulky ligands are required to isolate molecular homogeneous catalysts in order to prevent decomposition. Herein, we capitalize on the catalytic properties of Mn and circumvent the instability of these complexes through incorporation of Mn-atoms into porous crystalline frameworks, such as metal-organic frameworks (MOFs). MOFs are able to enhance the stability of these catalysts while also providing accessibility to the Mn sites for enhanced reactivity. We solvothermally synthesized two trinuclear Mn-based MOFs, namely [Mn₃O(BDC)₃(H₂O)₃] (Mn-MIL-88, where H₂BDC = benzene-1,4-dicarboxylic acid) and [Mn₃O(BDC-Me₄)₃(H₂O)₃] (Mn-MIL-88-Me₄, where H₂BDC-Me₄ = 2,3,5,6-tetramethylterephthalic acid). Through comprehensive single-crystal X-ray diffraction, spectroscopic, and magnetic studies, we revealed that both MOFs are in a Mn(II/III) mixed-valence state instead of the commonly observed Mn(III) oxidation state. Furthermore, the use of a methylated linker (BDC-Me₄) allowed access to permanent porosity in Mn-MIL-88-Me₄, which is an analogue of the flexible MIL-88 family, yielding a catalyst for alcohol oxidation.