The Synthesis, Structure And Characterization Of Functional Coordinated Compounds With Nano-size Channels Based On D And S Blocks Metal-Ions

Porous coordination polymers which possess of open regular frameworks are constructed by metal ions or Metal-Oxygen clusters and suitable organic ligands through the self-assembly. There are controllable structures, high porosity, regular channels and so on. In advance, we can pick up some construction models with special geometrical conformations and chemical characteristics, then design and synthesize them and finally obtain crystal materials with expectant functions utilizing their self-assembly.This paper decides to design and construct porous Metal-Organic Frameworks with nano-size channels from two aspects, namely, coordination polymers'two basic elements—organic ligands and metal centers (metal ions or Metal-Oxygen clusters). First, this paper designs and synthesizes two large organic ligands:L1,1,4-di-(1H-imidazol-4-yl)-benzene (or H2L1) and L2,4,4',4"-[1,3,5-benzenetriyltris-(carbonylimino)]trisbenzoic acid (or H3L2). Then, active traditional metal ions are used to react with each ligand under hydrothermal conditions to produce porous coordinated polymers, respectively. Second, this paper selects and uses less active alkaline earth metal ions interacting with suitable small organic ligands to research the synthesis of porous Metal-Organic Frameworks including light-metals under hydrothermal or gas-diffusion conditions. In conclusion, we obtain11coordination polymers with new structures. We also do some researches of IR, EA(elementary analysis), TG, PXRD, adsorption, fluorescence and magnetism characteristic of these coordinated compounds.Main work includes several parts as following:1. The synthesis and characteristics of L1,1,4-di-(1H-imidazol-4-yl)-ben-zene (or H2L1).2. The synthesis, characteristics and adsorption/magnetism researches of compound Co(H2L1)2(CH3COO)2(1) based on L1. This compound consists of3D framework with the interpenetrating of (4,4)-c net layers in different directions.3. The synthesis and characteristics of L2,4,4',4"-[1,3,5-benzenetriyltris(car-bonylimino)]trisbenzoic acid (or H3L2).4. The synthesis, characteristics and fluorescence researches of compounds Zn3(L23-)2(DMF)(H2O)2·5DMF·3H2O (2),(Zn4O)2(L23-)4(DMF)2(H2O)3· xGuest (3) and Zn(HL22-)(Py)(DMF)·DMF (4) based on L2. Both crystal2and3possess of3D frameworks with the2-fold interpenetrating of the (3,6)-c3D network containing large channels. The crystal4consists of one-dimension chains.5. The synthesis, characteristics and adsorption/fluorescence researches of compounds Mg3(PDC2)3(DMF)3·DMF (5), Sr(TPTA2)(DMF)(6), Ba (PDC2)(H2O)3(7), Ba(PDC2)(H2O)2(8), Ca(PDC2)(H2O)5·H2O (9), Ca(PDC2-)(H2O)2(10) and Mg(PDC2-)(H2O)2(11)(H2PDC—pyridine-3,5-dicarboxylic acid; H2TPTA—terephthalic acid) based on alkaline earth metal ions. The complex5containes a3D framework being constructed by8-connected Mg-O clusters and organic ligands, which includs two channels A and B (more than10A of the aperture). The structure6is composed of chiral Sr-O helix chains and organic ligands forming a3D porous coordinated polymer with triangle channels. And maybe it is just the formation of Sr-O chains in this structure that results in the very high thermal stability of the porous metal-organic framework. The crystal7and8are both constructed with Ba-O chains and organic ligands coming into being3D coordination polymers with different topological networks. These crystals9-11are three different low-dimensions coordination compounds.