The Structures And Properties Of Metal-organic Frameworks Based On 9,9’-spirobifluorene And Dibenzothiophene

Metal-Organic Frameworks(MOFs) is involved in this dissertation. We have designed and synthesized new ligand for the construction of MOFs with novel structures and properties.Three ditopic ligands have been synthesized, and they are 2,2’-9,9’-Spirobi[9H-fluorene]-dicarboxylic acid(2,2’-SBF-2COOH), 2,7-9,9’-Spirobi[9H-fluorene]-dicarboxylic acid(2,7-SBF-2COOH) and 2,8-Dibenzothiophene-dicarboxylic acid(2,8-DBT-2COOH). We have suggested rational routes, including hydrolysis of cyano group or oxidation of acetyl group, to the facile and efficient synthesis of these ligands.The new framework SHU-1 with a 2D hollow structure was constructed by 2,2’-SBF-2COOH and a novel square-planar Ca4 O cluster. A series of phase transitions has been observed for SHU-1. SHU-1 could be transformed into SHU-1a in methanol, and SHU-1a demonstrates a 2D layered structure with tubular void. Both SHU-1 and SHU-1a could be transformed into SHU-1b in water, and SHU-1b could be re-transformed into SHU-1a in methanol. SHU-1, SHU-1a and SHU-1b showed adsorption selectivity towards malachite green(MG). The thermodynamic and kinetic studies on the exothermic adsorption of MG indicated, SHU-1b could adsorb MG spontaneously. SHU-1b also showed reusability of MG adsorption. White light emission has been achieved by incorporating organic dyes into SHU-1b.We have obtained Zn-SBF-BPY starting from 2,7-SBF-2COOH. Zn-SBF-BPY showed a 2-fold interpenetrated 3D framework structure. The interdigitated structure with medium BET area and different pore sizes may be benefit for CO2 and H2 adsorptions.A metal organic polyhedron Cu-MOP constructed from 2,8-DBT-2COOH and Cu paddlewheel SBU with octahedral geometry has been synthesized and characterized. Cu-MOP showed gas adsorption properties of H2 and CO2. Taking the advantages of electron-donating DBT ligand, Cu-MOP could act as a solid reductant to reductively decompose TCNQ, DDQ, MB and CR.Zn-DBT with a ths topology has been constructed from 2,8-DBT-2COOH and Zn4 O SBU, and showed selective adsorption towards benzothiophene(BT).