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Synthesis and Characterization of Functionalized Metal-organic Frameworks
Published on: September 5, 2014
From 1D Coordination Polymers to Metal Organic Frameworks by the Use of 2-Pyridyl Oximes
Ioannis Mylonas-Margaritis1, Auban Gérard1, Katerina Skordi2
1School of Chemistry, College of Science and Engineering, National University of Ireland Galway, SSPC, Synthesis and Solid State Pharmaceutical Centre, University Road, Galway H91 TK33, Ireland.
Abstract:
The synthesis and characterization of coordination polymers and metal-organic frameworks (MOFs) has attracted a significant interest over the last decades due to their fascinating physical properties, as well as their use in a wide range of technological, environmental, and biomedical applications. The initial use of 2-pyridyl oximic ligands such as pyridine-2 amidoxime (H2pyaox) and 2-methyl pyridyl ketoxime (Hmpko) in combination with 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid), H4pma, provided access to nine new compounds whose structures and properties are discussed in detail. Among them, [Zn2(pma)(H2pyaox)2(H2O)2]n (3) and [Cu4(OH)2(pma)(mpko)2]n (9) are the first MOFs based on a 2-pyridyl oxime with 9 possessing a novel 3,4,5,8-c net topology. [Zn2(pma)(H2pyaox)2]n (2), [Cu2(pma)(H2pyaox)2(DMF)2]n (6), and [Cu2(pma)(Hmpko)2(DMF)2]n (8) join a small family of coordination polymers containing an oximic ligand. 9 exhibits selectivity for FeIII ions adsorption, as was demonstrated by a variety of techniques including UV-vis, EDX, and magnetism. DC magnetic susceptibility studies in 9 revealed the presence of strong antiferromagnetic interactions between the metal centers, which lead to a diamagnetic ground state; it was also found that the magnetic properties of 9 are affected by the amount of the encapsulated Fe3+ ions, which is a very desirable property for the development of magnetism-based sensors.

