Abstract

AbstractBifunctional ionic metal–organic frameworks (MOFs) containing Lewis acid sites (unsaturated metal sites) and halide ions (Cl−, Br−, and I−) have attracted increasing attention due to their extra high activity for the cycloaddition of CO2 with epoxides. Herein, a novel microporous MOF (1‐Eu), namely, [Eu3(L)2(HCOO)(H2O)5]·14H2O (H4L = 2,6‐di(2,4‐dicarboxyphenyl)‐4‐(pyridine‐4‐yl)pyridine), has been synthesized by using a new bipyridyl‐based tetracarboxylate ligands (H4L). Structural analyses show that 1‐Eu is a 3D framework in which 1D chains with alternating triple and single carboxylate bridges are interlinked by the L ligands and contains microporous channels with uncoordinated pyridyl N atoms, which are easy to be modified by N‐methylation. Therefore, three bifunctional N‐methylation 1‐Eu MOFs, 1‐Eu‐MeX (X = Cl−, Br−, and I−), were successfully prepared from the 1‐Eu MOF by a postsynthetic modification (PSM) method. 1‐Eu‐MeX can efficiently catalyze the cycloaddition reaction without any cocatalyst and solvent. Among them, the 1‐Eu‐MeI catalyst displays the highest catalytic performance. Our work thus represents a rare demonstration of ionic MOFs as heterogeneous catalysts for efficient CO2 fixation with epoxides. More significantly, 1‐Eu‐MeX are the first reported Eu‐based ionic MOFs with the bipyridyl‐based tetracarboxylate ligand.

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