在温和条件下催化二氧化碳转化为噁唑烷酮的高效桨轮铜簇基金属有机框架

IF 4 2区 化学 Q2 CHEMISTRY, PHYSICAL Journal of Molecular Structure Pub Date : 2024-11-05 DOI:10.1016/j.molstruc.2024.140607
Zhuo-Hao Jiao , Shuo Sun , Hua Li , Xiao-Na Gao , Zi-Qian Li , Yu-Heng Liu , Yan Fu , Lei Nie , Lei Wang
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摘要

高效利用二氧化碳并将其转化为高附加值产品有助于缓解温室效应等环境问题。在这些方法中,二氧化碳与丙炔胺的羧化环化反应是一种绿色且原子经济的方法。开发可在温和条件下促进该反应的高性价比催化剂是可取的,但具有挑战性。在此,我们合成了一种独特的二维(2D)金属有机框架(MOF){[Cu(QCA)2]∙0.5DMF∙0.5H2O}n (1)(QCA=6-喹啉羧酸,DMF=N,N-二甲基甲酰胺),并对其进行了全面表征。化合物 1 由桨轮双核铜簇 [Cu2(COO)4] 和羧酸配体构建而成,呈现出一种具有新拓扑结构的二维框架。稳定性测试表明,化合物 1 在不同溶剂中会发生可逆的结构变化,并表现出良好的热稳定性。1 作为异相催化剂,能在温和条件下将 CO2 和丙炔胺转化为噁唑烷酮,具有广泛的底物通用性。此外,1 还能在五个连续反应中保持其催化性能。这项工作展示了二维不含贵金属的 MOF 基催化剂在温和条件下表现出高催化效率的罕见实例。
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Efficient paddle-wheel copper cluster-based metal-organic framework for catalytic conversion of CO2 to oxazolidinones under mild conditions
Efficient utilization of CO2 and its conversion into high-value-added products contribute to mitigating environmental issues such as the greenhouse effect. Among these methods, the carboxylation cyclization of CO2 with propargylic amine represents a green and atom-economical approach. Developing cost-effective catalyst that can promote this reaction under mild condition is desirable but challenging. Herein, a unique two-dimensional (2D) metal–organic framework (MOF) {[Cu(QCA)2]∙0.5DMF∙0.5H2O}n (1) (QCA =6-quinolinecarboxylic acid, DMF = N,N-dimethylformamide) have been synthesized and thoroughly characterized. Compound 1 was constructed from paddle-wheel dinuclear copper clusters [Cu2(COO)4] and carboxylate ligands, presenting a two-dimensional framework with new topology. Stability tests indicate that compound 1 undergoes reversible structural changes in different solvents and exhibits good thermal stability. 1 as heterogeneous catalyst enabled the transformation of CO2 and propargylic amine into oxazolidinones under mild conditions with broad substrate generality. In addition, 1 could maintain its catalytic performance with five continuous reactions. This work presents an infrequent example of a 2D noble metal free MOF-based catalyst that shows high catalytic efficiency under mild conditions.
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来源期刊
Journal of Molecular Structure
Journal of Molecular Structure 化学-物理化学
CiteScore
7.10
自引率
15.80%
发文量
2384
审稿时长
45 days
期刊介绍: The Journal of Molecular Structure is dedicated to the publication of full-length articles and review papers, providing important new structural information on all types of chemical species including: • Stable and unstable molecules in all types of environments (vapour, molecular beam, liquid, solution, liquid crystal, solid state, matrix-isolated, surface-absorbed etc.) • Chemical intermediates • Molecules in excited states • Biological molecules • Polymers. The methods used may include any combination of spectroscopic and non-spectroscopic techniques, for example: • Infrared spectroscopy (mid, far, near) • Raman spectroscopy and non-linear Raman methods (CARS, etc.) • Electronic absorption spectroscopy • Optical rotatory dispersion and circular dichroism • Fluorescence and phosphorescence techniques • Electron spectroscopies (PES, XPS), EXAFS, etc. • Microwave spectroscopy • Electron diffraction • NMR and ESR spectroscopies • Mössbauer spectroscopy • X-ray crystallography • Charge Density Analyses • Computational Studies (supplementing experimental methods) We encourage publications combining theoretical and experimental approaches. The structural insights gained by the studies should be correlated with the properties, activity and/ or reactivity of the molecule under investigation and the relevance of this molecule and its implications should be discussed.
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