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Syntheses, Structures and Properties of Microporous Metal-Organic Frameworks

Author: QinJunSheng
Tutor: SunXiuYun；SuZhongMin
School: Northeast Normal University
Course: Physical and chemical
Keywords: Metal-organic frameworks (MOFs) Catalysis Luminescence
CLC: O641.4
Type: Master's thesis
Year: 2011
Downloads: 70
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Abstract


The aim of this thesis is the syntheses of novel porous coordination compounds by using different kinds of rigid and simi-rigid ligands through covalent linkage interaction. The study on synthetic conditions and rules for these new compounds and the exploration of relationships between structures and properties for these new compounds are also carried out.Fourteen new coordination compounds have been isolated on the basis of solvothermal technique and hydrothermal methods, and structurally characterized by elemental analyses, IR spectra, XRPD patterns, TG curves and single crystal X-ray diffractions. The thermal stabilities, catalysis activity, fluorescent activity of these compounds have been studied.1. Two microporous compounds have been obtained with the reation of H3BTC （1,3,5-Benzenetricarboxylic acid） and Mncl2 under solvothermal conditions at 95°C. [Mn3（BTC）2（H2O）3（DMF）3]n （1） [Mn4Cl（BTC）8/3]Cl2·H2O·2.5（DMF） （2） Compounds 1 and 2 exhibit cage-type structure with the size of 9×9 （?）2 and 15×15 （?）2, respectively. The adsorption ability of compound 1 toward dyes has been studied. Furthermore, the Mn-based metal-organic coordinations show good catalysis acticities. The catalysis desulfurization activity of compound 1 has been investigated.2. Reactions of lanthanide salts with the tripodal bridging ligand 5-（4-carboxy-phenoxy）-isophthalic acid （abbreviated as H3cpia） lead to the formation of a family of three-dimensional （4,8）-connected coordination polymers in the presence of formic acid or diethylamine. [La（cpia）（H2O）2]n·nH2O （3） [Ce（cpia）（H2O）2]n·nH2O （4） [Pr（cpia）（H2O）2]n·nH2O （5） [Nd（cpia）（H2O）2]n·nH2O （6） [Sm（cpia）（H2O）2]n·nH2O （7） [Eu（cpia）（H2O）2]n·nH2O （8） [Gd（cpia）（H2O）2]n·nH2O （9） [Dy（cpia）（H2O）2]n·nH2O （10） [Er（cpia）（H2O）2]n·nH2O （11） [Tm（cpia）（H2O）2]n·nH2O （12） [Y（cpia）（H2O）2]n·nH2O （13） X-ray crystal structure analyses revealed that compounds 3– 13 are isostructural only with slight differences in bond lengths and bond angles. A one-dimensional channel structure with dimensions of 9.46×11.42 （?）2 parallel to the b axis in compounds 3– 13. The luminescent spectra of solid 8 and 10 exhibit the characteristic emission of the Eu3+ ions and Dy3+ ions at room temperature.3. The reaction of znic and HATZ （5-Amino-tetrazole） under solvothermal conditions resulted in the formation of a molecular sieve-like coordination polymer with diamond topology. Zn（ATZ）2·DMA （14）Compound 14 shows a diamond topology metal-organic architechture with hexagonal channel.

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Structural Chemistry > Complex chemistry ( coordination chemistry )
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