Isoreticular Chiral Metal−Organic Frameworks for Asymmetric Alkene Epoxidation: Tuning Catalytic Activity by Controlling Framework Catenation and Varying Open Channel Sizes

A family of isoreticular chiral metal-organic frameworks (CMOFs) of the primitive cubic network topology was constructed from [Zn(4)(μ(4)-O)(O(2)CR)(6)] secondary building units and systematically elongated dicarboxylate struts that are derived from chiral Mn-Salen catalytic subunits. CMOFs 1-5 were synthesized by directly incorporating three different chiral Mn-Salen struts into the frameworks under solvothermal conditions, and they were characterized by a variety of methods, including single-crystal X-ray diffraction, PXRD, TGA, and (1)H NMR. Although the CMOFs 1 vs 2 and CMOFs 3 vs 4 pairs were constructed from the same building blocks, they exhibit two-fold interpenetrated or non-interpenetrated structures, respectively, depending on the steric sizes of the solvents that were used to grow the MOF crystals. For CMOF-5, only a three-fold interpenetrated structure was obtained due to the extreme length of the Mn-Salen-derived dicarboxylate strut. The open channel and pore sizes of the CMOF series vary systematically, owing to the tunable dicarboxylate struts and controllable interpenetration patterns. CMOFs 1-5 were shown to be highly effective catalysts for asymmetric epoxidation of a variety of unfunctionalized olefins with up to 92% ee. The rates of epoxidation reactions strongly depend on the CMOF open channel sizes, and the catalytic activities of CMOFs 2 and 4 approach that of a homogeneous control catalyst. These results suggest that, although the diffusion of bulky alkene and oxidant reagents can be a rate-limiting factor in MOF-catalyzed asymmetric reactions, the catalytic activity of the CMOFs with large open channels (such as CMOFs 2 and 4 in the present study) is limited by the intrinsic reactivity of the catalytic molecular building blocks. The CMOF catalysts are recyclable and reusable and retain their framework structures after epoxidation reactions. This work highlights the potential of generating highly effective heterogeneous asymmetric catalysts via direct incorporation of well-defined homogeneous catalysts into framework structures of MOFs.