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Topological Structural Design and Properties of Metal-Organic Crystalline Material

Author: KeXiJun
Tutor: LiDongSheng
School: Three Gorges University
Course: Mechanical Manufacturing and Automation
Keywords: Crystalline material Crystal structure Topological network Photoluminesence Magnetic property
CLC: O627
Type: Master's thesis
Year: 2011
Downloads: 75
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Abstract


Metal organic crystaline materials has been attracting a great attention of the researchers from the field of international materials, physics, chemistry, biology and medical science because of its controllable preparation based on the concept of molecule design and peculiar physical and chemical properties. And in addition, this type of materials shows splendid perspective of application in the aspect of gas adsorption storage, catalysis, molecular magnet, electron spin materials, flourescent materials, nonlinear optical materials, gas-sensitive materials and humidity sensitive materials, thus it become the frontiers of material research in recent years.The aim of this thesis is to construct the crystaline materials on the basis of high symmetrical semi-rigid organic molecular blocks and transitional metal centers or multi-nuclear metal-oxygen clusters, to study the synthetic conditions and constructing rules for these crystaline materials, probe into the structure of topological networks and their topological types, explore the possibility and feasibility of predesign for the new entangled networks and topological structures, to inspect the intermolecular forces （including the covalent bond and hydrogen bond）, the configuration of ligands, the influence of second ligands on the whole topological networks, and to preliminarily investigate the internal relationships between structures and properties for the new crystaline extended materials.Nineteen new metal organic crystaline materials have been synthesized by harnessing the hydrothermal technique and/or water solution synthesis methods on the concept of topological structural design and structurally characterized by elemental analyses, IR, XRPD, TG and single crystal X-ray diffractions. The thermal stabilities, magnetic properties and fluorescent activity of these compounds have been studied.Firstly, this thesis presents the preparation of five crystalline materials constructed from the Molecular Building Block （MBB） of high-symmetrical tetradentate squarate, emphatically discusses their topological structures. Crystalline materials [Cd（C4O4）（btab）·2H2O]n （1） and [Zn（C4O4）（bbi）·2H2O]n （2） are isostructural 2D （4,4） lattice plane coordinating network, and possesses the structural feature of inclined interpenetration of 2D→3D. Crystalline materials [Zn（C4O4）0.5·OH]n （3） is the third three nodal （3,6,6）-connected 3D 3,6,6T2 topological network. Crystalline materials {[Cd（ C4O4）（dpa）·2H2O]·3H2O}n （4） and {[Cd2（C4O4）2（C2O4）2（dpa）2·2H2O]·4H2O}n （5） are botained under the same experiment program and condition. Both of them show completely different structural dimensionality, namely, 4 displays the 2D （4,4） lattice plane coordinating network; while 5 exhibits the usual diamond topological network. The hydrogen bonding topological structural analysis for the lower dimentional 1 and 2 demonstrate that both of them are characterized by the unreported novel double nodal （4,6）-connected 3D hydrogen bonding self-penetration. Moreover, part of fluorescent properties for the above mentioned crystal materials were investigated.Secondly, this thesis presents the preparation of five crystalline materials constructed from the Molecular Building Block （MBB） of semirigid aromatic azo-conjugated tetracarboxylic acid, emphatically discusses their topological structures. Crystalline materials {[Zn（abtc）0.5（btab）]·2H2O}n （6） and {[Zn（abtc）0.5（bib）]·3H2O}n （7） are isostructural 3D 86 coordinating network, which is the first double nodal 4,4-cnnected 86 self-penetrating topological network simultaneously constructed from the distorted tetrahedron 4-cnnected node and plane 4-cnnected node. Crystalline materials [Cu（abtc）0.5（bip）·H2O]n （8） and {[Zn（abtc）0.5（bip）]·H2O}n （9） are also isostructural 3D coordinating network. After analysis and retrieval, we found it is the third bbf network possessing the interpenetrating feature. Crystalline materials [Co（H2abtc） （bpy）0.5·H2O]n （10） is characterized by the 2D interpenetrating honeycomb-like hexagon hcb topological srtucture. The 2D interpenetrating corrugated layers furtherly form the 3D supermolecule structure through theπ-πinteraction. Crystalline materials [Co2（H2abtc）1.5（btab）0.5·3H2O]n （11） possesses the structural feature of 3D tri-fold interpenetration. Regarding singel cobalt metal center as the node, 11 is the fifth （4,4）-connected rare tri-fold interpenetrating mog topological network. Considering the trinuclear cobalt clusters as the node, 11 displays an usual 6-connected tri-fold interpenetratingα-Po topological network with the point symbol 412. 63. Crystalline materials {[Cu4（abtc）2（btab）6·3H2O]·2H2O}n （12） is the multi-nodal 3D self-penetrating coordinating network. Regarding singel copper metal center as the node, 12 is a three nodal （4,4,5）-connected self-penetrating topological network. Considering the dinuclear copper clusters as the node, 12 displays a three nodal （4,4,8）-connected self-penetrating topological network. After analysis and retrieval, we found both of them are new types of self-penetrating topological networks. Crystalline materials [Mn（H2abtc）（H3abtc）（bpy）·H2O]n （13） is zero dimensionality supermolecule structure. The hydrogen bonding topological structural analysis for 13 demonstrates that it is characterized by the usual single nodal 6-connected 3D interpenetratingα-Po hydrogen bonding topological network. Crystalline materials [Mn（H2abtc）（bdt）·2H2O]n （14） is 2D （4,4） lattice plane coordinating network. Similarly, the hydrogen bonding topological structural analysis for 14 was executed, and the result indicates that it is an unreported three nodal multifold mixed high connected （6,8,8）-connected hydrogen bonding self-penetrating structure. After analysis and retrieval, we found it is the new topological type. Besides, part of magnetic properties or fluorescent properties for the above mentioned crystal materials were investigated. Some results indicate that crystalline materials 10 and 11 shows weak antiferromagnetism, while 12 displays ferromagnetism. Part of research results have been published in the international professional journal:CrystEngComm 2011, 13, 3355-3359; （IF=4.18）和Inorg.Chem.Commun. 2011, 14, 778-803; （IF=2.08, Invite review）.Finally, this thesis presents the preparation of five crystalline materials constructed from the Molecular Building Block （MBB） of semirigid aromatic azo-conjugated hexacarboxylic acid or aromatic dicarboxylic or tricarboxylic acid transformed from the in situ reaction of aromatic azo-conjugated hexacarboxylic acid, emphatically discusses their topological structures. Crystalline materials {[Mn3（abhca）（bix）2·2H2O]·4H2O}n （15） is the multi-nodal 3D coordinating network. Regarding singel manganese metal center as the node, 15 is a three nodal （4,4,8）-connected topological network. Considering the trinuclear manganese clusters as the node, 15 displays a double nodal （4,8）-connected topological network. After analysis and retrieval, we found both of them are new types of topology. Crystalline materials [Cd3（nbtc）2·4H2O]n （16） is a new three nodal （3,4,9）-connected 2D coordinating network. While Crystalline materials [Cu3（hnipO）2·（H2O）3]n （17） is an usual （3,4）-connected 2D coordinating network. Notably,the 3D microporous metal-organic framework of 16 and 17 are constructed from the 2D coordinating layers struted by the hydrongen bond interaction. Crystalline materials [Cu2（hnipO）2（dpa）·2H2O]n （18） is zero dimensionality supermolecule structure. The hydrogen bonding topological structural analysis for 18 demonstrates that it is characterized by the usual single nodal 6-connected 3D hydrogen bonding bsn topological network. Crystalline materials [Cu3（hnipO）2（btab）]n （19） is a 3D coordinating network. Regarding singel copper metal center as the node, 19 is a double nodal （3,6）-connected topological network. Considering the secondary building units {Cu2（hnipO）2} as the node, 19 is a very common double nodal 4,6-connected self-penetrating fsc topological network. Remarkably, comparing the double nodal （4,6）-connected self-penetrating topological networks from 1 and 19 respectively, we find both of them share completely similar topological point symbol, however, utterly different topological vertex symbol. And the former is a 3D hydrogen bonding self-penetrating network, while the latter 3D coordinating self-penetrating network. Besides, part of magnetic properties or fluorescent properties for the above mentioned crystal materials were investigated. Some results indicate that crystalline materials 18 and 19 shows different degree of antiferromagnetism. Part of research results have been published in the international professional journal:Inorg. Chem. Commun., 13 （2010） 484-487; IF=2.08.In conclusion, this thesis has obtained some new topological networks model, especially found and establishied five types of novel self-penetrating entanglent toplogical networks, where there are three types of 3D coordinated self-penetrating networks （for crystalline materials 6, 7 and 12） and two types of 3D hydrogen bonding supermolecule self-penetrating networks （for crystalline materials 1, 2 and 14）. And in addition, the relationship between structures and properties for part of crystalline materials has been preliminarily probed. The work of this thesis contributes some new experiment data and network models to the fertility of current topological networks data base, and provide some significative theoretical foundation for the topological structural design and constructing modification of the crystalline materials oriented by the anticipated functionality.

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CLC: > Mathematical sciences and chemical > Chemistry > Organic Chemistry > Elements in organic compounds
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