The target for the self-assembly of functional microporous metal-organic frameworks (MOFs) could be realized by employing ligand-directed and/or template-induced strategies, which prompted us to explore the synthetic technique of d secondary-building-unit-based nanoporous frameworks. Here, the exquisite combination of a paddle-wheel [Mn(CO)(OH)] cluster and a TDP ligand contributes one robust honeycomb framework of {(MeNH)[Mn(TDP)(HO)]·3HO·3DMF} (; DMF = ,-dimethylformamide), whose activated state with the removal of associated aqueous molecules characterizes the outstanding physicochemical properties of nanochannels, penta- and tetracoordinated Mn serving as highly open metal sites, rich Lewis base sites (rows of C═O groups and N atoms), and excellent thermal stability. Moreover, it is worth mentioning that Lewis acid-base sites on the inner surface of the channels in activated successfully form one unprecedented canal-shaped acid-base confined space with evenly distributed open metal sites of Mn and N atoms as the canal bottom as well as two rows of C═O groups serving as dyke dams. Catalytic experiments displayed that activated could serve as an efficient heterogeneous catalyst for the chemical fixation of CO with epoxides into cyclic carbonates under mild conditions. Furthermore, could effectively catalyze the reaction Knoevenagel condensation, which should be ascribed to the synergistic polarization effect aroused from its plentiful Lewis base sites in the confined channel space. Hence, these results demonstrate that the employment of ligand-directed and template-dependent strategies could overcome the self-assembled barriers of functional microporous MOFs and achieve unexpected frameworks.
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http://dx.doi.org/10.1021/acs.inorgchem.1c00352 | DOI Listing |
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