Design, Synthese And Property Study Of Metal-organic Frameworks Based On Metal Oxide Clusters

Metal-organic frameworks (MOFs), is another important and novel porous materialafter zeolites and carbon materials. This kind of material possesses many advantages,for example, very mild reaction conditions, the diversity of the structure, and so on.However, this material also has a drawback: the stability is not very good. Currently,the materials are widely used in catalysis, energy storage and separations. A few yearsago, most researchers focused on the experimental and theoretical studies of gasstorage. After removal of guest molecules inside such materials, the pores can remainthe integrity of the skeleton. Therefore, many potential special properties anout MOFsshould be further studied, containing the selective catalysis, sensing, reversiblehost-guest molecules (ions) exchange, energy conversion and storage, separation,optical materials, magnetic materials and biological applications, and this materialsexhibit attractive prospect in the development of new porous materials.In this dissertation, we use some common organic ligands and metal ions to designand synthesize ten kinds of metal-organic framework. The study about therelationship between synthesis conditions and skeletons, topological analysis, theimpact of the ancillary ligands on the entire structure are carried out. Therefore, somebasic physical properties, for example, thermal stability of the skeleton, biologicalapplications (drug loading and release properties), and magnetic properties of themare also studied. These findings include the following four aspects:1. By means of the stepwise strategy, the reaction between a series of linearligands and metal-organic polyhedra as precursors generate four MOFs undersolvothermal reactions.12coordinated water molecules outside the metal-organicpolyhedra are replaced by the linear ligands, generating the12-connected frameworkwith fcu topology. The Schl fli symbol is (324·436·56). In these compounds, themicropore and mesopores exist, and the same channels run along the a, b, and cdirections{[Cu24(5-NH2-mBDC)24(bpy)6(H2O)12]·72DMA}(1){[Cu24(5-hip)24(pz)6(H2O)12]·64DMF}(2){[Cu24(5-hip)24(bpy)6(H2O)12]·119DMF}(3){[Cu24(5-hip)24(bpe)6(H2O)12]·138DMF}(4)5-NH2-mBDC=5-aminoterephthalic acid 5-hip=5-hydroxyisophthalic acidpz=Pyrazinebpy=4,4’-bipyridinebpe=1,2-di(pyridin-4-yl)ethene2. Three allomorphs with the same stoichiometry were solvothermally synthesizedin the presence of different additives. All of them possess one-dimensionalnanotubular channels with rhombic shapes，which are constructed from trinuclearclusters and angular bidentate organic linkers. The nanotubes are further held togetherthrough edge sharing modes forming a new3D network. The overall3D network canbe rationalized as a uninodal8-connected bcu topology with Schl fli symbol (424·64).[Mg3(H2O)4(5-aip)2(5-Haip)2]·4DMA (5)[Mg3(H2O)4(5-aip)2(5-Haip)2]·4DMA (6)[Mg3(H2O)4(5-aip)2(5-Haip)2]·4DMA (7)5-aip=5-aminoterephthalic acid3. Herein, we demonstrate that the varying amount of NaOH can be successfullyused to achieve three structures. Considering that two of them have been reported,there are no descriptions here.8consists of four kinds of second building units(SBUs). These SBUs along with BTC ligands construct two types of cages. Twolayers generate through the different arrangements of cages. Naturally, the wholestructure can be described as alternating arrangements of cage layer and channel layer.The overall structure is a3D (3,4,6)-connected network with a Point symbol(4·62)4·(4·82)8·(62·84)·(86)2·(43·64·88)4.[Zn10(OH)O(BTC)5(HBTC)(DMA)2(H2O)4]·11DMA (8)BTC=Trimesic acid4. In the presence of the aminosalicylic acid, we successfully isolate two newporous coordination polymers based on situ hexa-cobalt clusters. Compound9createsa regular3D structure with different channels along a, b, and c axes. These channelsare perpendicular to each other, and interconnected to form a3D intersecting porousframework. While,10exhibits1D small channels stacking along the c axis. Theoverall3D nets can be rationalized as a uninodal6-connected framework with thepoint symbol of (44·610·8).[Co6(μ3-OH)2(ip)5(H2O)3]·7DMA (9) [Co3(μ3-OH)(ip)2.5(H2O)(DMF)]·2DMF (10)ip=isophthalic acid...