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Syntheses, Structure and Properties of Metal Complexes with Imidazoledicarboxylic Acid and Aromatic Multicarboxylic Acid

Author: LuoZhiRong
Tutor: YinXianHong
School: Guangxi University for Nationalities
Course: Applied Chemistry
Keywords: Imidazoledicarboxylic acid Aromatic carboxylic acid Crystal structures Thermal stability Coordination compounds
CLC: O621.13
Type: Master's thesis
Year: 2011
Downloads: 237
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Abstract


2-propyl-4,5-imidazoledicarboxylic acid belongs to a ligand that is easy to form an organic chiral, a spatial grid-like or a spiral structure of the compounds. The coordination modes of aromatic carboxylic acids are versatile, so the structures of coordination polymers based on aromatic carboxylic acids and rare earth are more complicated and novel. Being attracted much people’s attention and interests, the metal complexes of the carboxylic acid have the potential diversity of structure and magnetic properties, adsorption, catalytic and luminescence and so on. Therefore, systematic studies have been carried out in this paper by reaction of transition metal and rare-earth metal, 2-propyl-4,5-imidazoledicarboxylic acid or benzene-1,2,4,5-tetracarboxylic acid, benzene-1,3,5-tricarboxylic acid and a series of N-donor ligands to investigate and discuss the difference substituents on the properties and construction of coordination complexes. We have synthesized sixteen complexes by solution and hydrothermal methods, which have been chatacterized by elemental analysis, X-Ray diffraction, FT-IR spectrum. The thermal stability(the complexes of 1-6 and 8-13) and electrochemistry(the complexes of 2, 4, 6, 7, 12 and 13) have been also presented.There are six chapters in this dissertation:In the first chapter, we introduce the development of coordination complexes about the properties of luminescence, magnetics, catalysis and adsorption, as well as the reseach significance and the result of this thesis.In the second chapter, 2-propyl-4,5-imidazoledicarboxylic acid has been selected as ligand and four novel complexes have been designed and synthesized with Zn(II) and Co(II) salts, namely [M(H2pimca)2 (H2O)2]·4H2O (1, 2) and [Co(H2pimca)2(H2O)2]·2DMF (3, 4) (M = Zn, Co). We describe their synthesis, IR spectra, crystal structures, thermal stability as well as the electrochemical studies of complexes 2 and 4.In the third chapter, 2-propyl-4,5-imidazoledicarboxylic acid has been selected as ligand and six novel complexes have been designed and synthesized with Na(I), Cu(II), Cd(II), Pb(II), Ca(II) and Mn(II) salts, namely {Na2[(H2pimca)(H2O)]2·H2O}n (5), [Cu(H2pimca)2]n (6), [Cd (H2pimca)2]n (7), [Pb(H2pimca)2(H2O)2]n (8), [Ca(H2pimca)2(H2O)2]n (9) and {[Mn3(pimca)2(H2O)5]·H2O}n (10). The complexes of 5-8 have been synthesized by solution methods, and the complexes of 9-10 have been synthesized by hydrothermal methods. We describe IR spectra, crystal structures, thermal stability (except 7) as well as the electrochemical studies of complexes 6 and 7.In the fourth chapter, complexes 11 and 12 belong to mononuclear complexes, complex 13 is a coordination polymer. The complexes of 11 and 13 have been synthesized with 2-propyl-4,5-imidazoledicarboxylic acid and bipyridyl, namely [Zn(H2pimdc)2(2,2′-bpy)(H2O)] (11) and {[Cu2(Hpimdc)(4,4′-bpy)]·H2O}n (13), the complex [Zn(Hoba)2(4,4′- bpy)2] (12) has been synthesized with 4,4’-oxydibenzoic acid and 4,4′-bpy. We describe IR spectra, crystal structures, thermal stability as well as the electrochemical studies of complexes 12 and 13. The complex 11 forms a zig-zag via multiple hydrogen bonds and C-H…πinteractions. The complex 12 forms a 2D network like rhombus via hydrogen bonds (O-H…N). The compound 13 form 1D chain topology geometry.In the fifth chapter, benzene-1,2,4,5-tetracarboxylic acid and benzene-1,3,5-tricarboxylic acid have been selected as ligands and three novel complexes, namely {[Er(C10H4O8)0.5(C10H2O8)0.5(H2O)2]·(H2O)4}n (14), [Dy(C9H3O6)(H2O)]n (15), {[Gd(C10H2O8)0.5(C2O40.5 (H2O)2]·2H2O}n (16), have been designed and synthesized with rare earth oxide (Er2O3, Dy2O3 and Gd2O3), which have been chatacterized by elemental analysis, X-Ray diffraction, FT-IR spectrum. The complex 14 forms fish-net topology geometry. The complex 15 forms a 3D micropore metal-organic framework, the total potential solvent accessible void volum of pore is 626.8 ?3 by calculating with platon software. If the coordination water molecule is removed, the total potential solvent accessible void volum of pore is 730.1 ?3 via calculating with platon software. The complex 16 forms a cubic net topology geometry. The oxalic acid and benzene-1,2,4,5-tetracarboxylic acid link the Gd(III) ion alternately.In the sixth chapter, we summarize the achievements and defects systematically in the paper, and put forward proposals and expectations in the future.

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CLC: > Mathematical sciences and chemical > Chemistry > Organic Chemistry > Organic Chemistry general issues > Theory of organic chemistry,physical organic chemistry > Organic Chemistry Structure Theory
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