Abstract
Emerging new metal-organic structures with tunable physicochemical properties is an exciting research field for diverse applications. In this work, a novel metal-organic framework Cu(HIT)(DMF)0.5, named URJC-1, with a three-dimensional non-interpenetrated utp topological network, has been synthesized. This material exhibits a microporous structure with unsaturated copper centers and imidazole–tetrazole linkages that provide accessible Lewis acid/base sites. These features make URJC-1 an exceptional candidate for catalytic application in acid and base reactions of interest in fine chemistry. The URJC-1 material also displays a noteworthy thermal and chemical stability in different organic solvents of different polarity and boiling water. Its catalytic activity was evaluated in acid-catalyzed Friedel–Crafts acylation of anisole with acetyl chloride and base-catalyzed Knoevenagel condensation of benzaldehyde with malononitrile. In both cases, URJC-1 material showed very good performance, better than other metal organic frameworks and conventional catalysts. In addition, a remarkable structural stability was proven after several consecutive reaction cycles.
Highlights
Metal–organic framework (MOFs) materials have been intensively exploited in terms of using a considerable variety of organic ligands containing oxygen, nitrogen, sulfur, or phosphorus as donor atoms to coordinate the metal or metal clusters [1]
N-substituted azole compounds like N-substituted tetrazole heterocycles, can present intrinsically basic properties [9]
The crystalline structure of URJC-1 material was solved by the single crystal X-ray diffraction technique resulting in a three-dimensional non-interpenetrated utp or (10,3)-d topological network [29]
Summary
Metal–organic framework (MOFs) materials have been intensively exploited in terms of using a considerable variety of organic ligands containing oxygen, nitrogen, sulfur, or phosphorus as donor atoms to coordinate the metal or metal clusters [1]. Carboxylate-based MOF materials typically possess low chemical stability in dilute acidic and basic media and are sensitive to moisture [2], being hydrolyzable and, not suitable for many industrial applications. In this sense, azole compounds are considered promising organic ligands for the construction of MOFs due to their great diversity [3,4] and high coordination ability for bridging metal ions, providing strong metal–nitrogen interactions [5,6,7,8]. Copper-based MOF materials with unsaturated metal centers
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