Metal–Organic Frameworks with Pyridyl-Based Isophthalic Acid and Their Catalytic Applications in Microwave Assisted Peroxidative Oxidation of Alcohols and Henry Reaction

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• 作者：Anirban Karmakar ; Luísa M. D. R. S. Martins ; Susanta Hazra ; M. Fátima C. Guedes da Silva ; Armando J. L. Pombeiro
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：April 6, 2016
• 年：2016
• 卷：16
• 期：4
• 页码：1837-1849
• 全文大小：783K
• ISSN：1528-7505

文摘

Reactions of 5-{(pyridin-4-ylmethyl)amino} isophthalic acid (H₂L1) with copper(II), zinc(II), and cadmium(II) were studied, and the obtained metal–organic frameworks (MOFs) [{Cu(L1)(DMF)}·DMF·H₂O]_n (1), [Zn(L1)(H₂O)]_n (2), and [Cd(L1)]_n (3) were characterized by elemental analysis, Fourier transform infrared spectroscopy, and X-ray single-crystal diffraction. As shown by X-ray crystallography, novel hybrid organic–inorganic coordination-driven assemblies were obtained which exhibit different two- and three-dimensional (2D and 3D) polymeric architectures. Compounds 1 and 2 have 2D structures, whereas compound 3 features a 3D network type polymer with a dimetallic core acting as a secondary building unit. These frameworks act as heterogeneous polymeric solid catalysts (the most effective one being the copper MOF 1) for solvent-free microwave assisted peroxidative oxidation of primary and secondary alcohols. They also effectively catalyze the nitroaldol (Henry) reaction of different aldehydes with nitroalkanes in water. These MOF-based heterogeneous catalysts can be easily recovered and reused, at least for a few consecutive cycles, without losing activity.