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Synthesis, Structure and Magnetic Properties of Metal Coordination Polymers with Tetrazole-1-Propanoic

Author: WangJianGuo
Tutor: SuZhongXing; LiuXiang
School: Lanzhou University
Course: Physical and chemical
Keywords: Coordination polymer tetrazole-1-propanoic acid Crystal StructuresMagnetic properties
CLC: O634
Type: Master's thesis
Year: 2012
Downloads: 102
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Abstract


Recently, the design and synthesis of carboxylate-tetrazole coordination compounds have been of an attractive area of research due to their intriguing topological structure as well as their novel physical properties such as anion exchange, photoluminescence, magnetism behavior and biological activities etc. In this thesis, we selected a multifunctional ligand, tetrazole-1-propanoic acid (Htzp),to construct novel transition coordination polymers. The selection of this ligand was based on the following considerations:(ⅰ) tetrazole-1-propanoic acid, with both carboxylate group and tetrazole ring, is expected to exhibit more varied coordinating patterns in the construction of multidimensional coordination frameworks;(ⅱ) the-(CH2)2-spacer between the tetrazole ring and carboxylate donor group offers flexible orientations of the carboxylate arm, favoring the formation of varied framework structures,(ⅲ) To our best knowledge, coordination polymers based on Htzp have not been reported so far. The main contributions in this thesis are blow:In the section1,five new Htzp-based coordination polymers{[Cd(tzp)2(2,2’-bpy)](ClO4)}n1,[Cd(Htzp)2(SCN)2]n2,[Cu3(tzp)4(H2O)2]n3,[Cu2(tzp)2(Cl)2]n4,[Ni(tzp)2]n5were synthesized and characterized by IR spectra, thermogravimetric analysis, single-crystal X-ray diffraction and magnetic property. In Complex1, two neighboring Cd(Ⅱ) ions are bridged by N and O atoms from Htzp ligand, forming a one-dimensional chain structure. Complex2displays a2-D layer structure by SCN ions bridging. Complex3and4is a2-D layer structure, complex3contain O(H2O) bridge and O(carboxy)bridge while complex4contain Cl bridge and O(carboxy) bridge. Complex5is a1-D Ni chain based on the paddlewheel-like [Ni2(tzp)4] building blocks. There are seven kinds of coordination modes of Htzp in complexes1-5, Based on the analysis of the crystal structures, the type of their hydrogen bonding,π-π stacking interaction and supramolecular structure were full discussed. Our research results indicate that, as a promising new type of multifunctional ligand, Htzp has a great potential in the filed of coordination polymers.Moreover, the magnetic properties of complexes3-5have been studied. The result shows a antiferromagnetic interaction between the Cu(Ⅱ) ions in the complex3;Variable-temperature magnetic susceptibility measurements of complex4showed ferromagnetic intramolecular coupling between the copper(Ⅱ) atoms; In complexes5, the magnetic data exhibited strong intramolecular antiferromagnetic interaction between the Ni(Ⅱ) ions. The structural and magnetic results are compared with those for other related dimmers.

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