A Porphyrin‐Based Porous rtl Metal–Organic Framework as an Efficient Catalyst for the Cycloaddition of CO 2 to Epoxides

A porous rtl metal–organic framework (MOF) [Mn 5 L(H 2 O) 6 ⋅(DMA) 2 ]⋅5DMA⋅4C 2 H 5 OH ( 1⋅ Mn) (H 10 L=5,10,15,20‐tetra(4‐(3,5‐dicarboxylphenoxy)phenyl)porphyrin; DMA= N , N ′‐dimethylacetamide) was synthesized by employing a new porphyrin‐based octacarboxylic acid ligand. 1⋅ Mn exhibits high Mn II density in the porous framework, providing it great Lewis‐acid heterogeneous catalytic capability for the cycloaddition of CO 2 with epoxides. Strikingly, 1⋅ Mn features excellent catalytic activity to the cycloaddition of CO 2 to epoxides, with a remarkable initial turnover frequency 400 per mole of catalyst per hour at 20 atm. As‐synthesized 1⋅ Mn also exhibits size selectivity to different epoxide substrates on account of their steric hindrance. The high catalytic activity, size selectivity, and stability toward the epoxides on catalytic cycloaddition of CO 2 make 1⋅ Mn a promising heterogeneous catalyst for fixation and utilization of CO 2 .