Highly Robust 3s-3d {CaZn}-Organic Framework for Excellent Catalytic Performance on Chemical Fixation of CO and Knoevenagel Condensation Reaction.

In terms of ligand-directed synthetic strategy, multifunctional metal-organic frameworks (MOFs) could be assembled by employing organic ligands with nitrogen-containing heterocycles, which could serve as Lewis base sites in crystallized porous frameworks. Here, the acidic one-pot hydrothermal reaction of CaCl, Zn(NO), and 2,4,6-tri(2,4-dicarboxyphenyl)pyridine (HTDP) generates one robust honeycomb-shaped double-walled material of {[(CH)NH][CaZn(TDP)(HO)]·3DMF·3HO} (), which has the excellent physicochemical characteristics of nanoscopic channels, high porosity (58.3%), large specific surface area, and high heat/water-resisting property. To the best of our knowledge, this is the first 3s-3d dinuclear [CaZn(CO)(OH)]-based nanoporous host framework, whose activated state possesses the coexistence of Lewis acid-base sites including four-coordinated Zn ions, four-coordinated Ca ions, uncoordinated carboxyl oxygen atoms, and N atoms. As expected, because of the coexistence of Lewis acid-base nature, desolvated displays satisfactory catalytic activity on the chemical cycloaddition of various epoxides with CO into the corresponding alkyl carbonates under comparatively mild conditions. Furthermore, the efficient conversion of benzaldehydes and malononitrile confirms that is simultaneously a bifunctional heterogeneous catalyst for Knoevenagel condensation reactions. Hence, the achievements broaden the way for assembling nanoporous multifunctional MOFs by employing ligand-directed synthetic strategy, which can accelerate the transformation from simple structural research to socially demanding applications.