A Porous Metal–Organic Framework Assembled by [Cu₃₀] Nanocages: Serving as Recyclable Catalysts for CO₂ Fixation with Aziridines

Abstract

Based on a novel ligand 5‐(2,6‐bis(4‐carboxyphenyl)pyridin‐4‐yl)isophthalic acid (H4BCP) with large skeletons, a unique porous framework {[Cu2(BCP)(H2O)2]·3DMF}n (1) assembled by nano‐sized and censer‐like [Cu30] cages is successfully obtained and structurally characterized. In 1, the large 1D channel in frameworks and window size in the nanocages can enrich methylene blue and capture CO2, exhibiting the promising applications in environmental protection. More importantly, the explorations on the cycloaddition reaction of CO2 and aziridines with various substituents suggest that 1 can serve as an efficient heterogeneous catalyst for CO2 conversion with aziridines in a solvent‐free system, which can be reused at least ten times without any obvious loss in catalytic activity. This is the first example of metal–organic framework (MOF)‐based catalysts in converting CO2 into high‐value oxazolidinones through activating aziridines and CO2, further extending the applications of MOFs materials in catalysis.

Valorization of Carbon Dioxide into Oxazolidinones by Reaction with Aziridines

“…In 2016, Liang-Nian He et al reported the first MOF catalyst for aziridine conversion into oxazolidinones, and reported that a [Cu30] nanocage based MOF ([Cu2(BCP)(H2O)2]•3DMF)n 13, (Scheme 5) could be used up to ten times without losing catalytic activity and showed high regioselectivity. [38] Optimum conditions however were 100 °C and 20 bar of CO2 for maximum conversions. This catalyst was more active than standard copper salts, but was arguably as active as the standard Copper MOF HKUST.…”

A Copper Metal–Organic Hydrogel as a Catalyst for SO2 and CO2 Fixation under Ambient Conditions

“…We then proceeded to test the efficacy of the xerogel as a catalyst for the reaction of SO 2 and CO 2 with epoxides for their chemical fixation. In recent years, copper‐containing MOFs have been shown to catalyze the chemical fixation of CO 2 , . However, it is worth mentioning that the synthesis of MOGs is more straightforward as compared to the synthesis of MOFs.…”

Solvent-free incorporation of CO2 into 2-oxazolidinones: a review

“…In 2016, Zhao and He along with their co-workers prepared a unique porous framework {[Cu 2 (BCP)(H 2 O) 2 ]$3DMF}n(H 4 BCP ¼ 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid) with 30-nuclear copper nanocages by solvothermal methods. 38 The metal-organic framework was reported to be an efficient and environmentally friendly catalyst for the coupling of 1-alkyl-2arylaziridines 24 with CO 2 (2 MPa) in the presence of tetrabutylammonium bromide (TBAB) as a co-catalyst under solvent-free conditions (Scheme 12). The MOF could be recovered by centrifugation and ltration, and efficiently reused for 10 catalytic cycles without any obvious loss in catalytic activity.…”