Syntheses And Properties Of Metal-organic Crystalline Materials Based On Conjugated Carboxylate Ligands

Based on the applications and functionality of metal-organic crystalline materials，wefocus our research on the synthesis, topological networks and functional properties of thesematerials. The aims are to explore the diversified structure of metal-organic crystallinematerials and to examine the organic ligands of different configurations and metal centersof the different coordination modes to the role of the structure. We can realizeprogressively the metal-organic crystalline materials of the semi-directional and directedsynthesis. In this paper, the transition metal ions and the lanthanide metal ions wereselected as templates, and two kinds of conjugated carboxylates ligands were chosen aslinkers to construct seventeen metal-organic crystalline materials with novel structures.Their topological structures and multifunctional properties have been explored. Theseresults will be introduced from the following three issues:Firstly，by using squaric acid and transition metal salts，four crystalline materials havebeen synthesized under hydrothermal condition. Structural analyses reveal that crystallinematerials1displays a3D3,6,6T2topological network. Crystalline materials2shows a3D4,5,6-connected4,5,6T32net. Crystalline materials3features a2D44-sql network. Andcrystalline materials4is2D (4,4) lattice plane coordinating network, and possesses thestructural feature of inclined2Dâ†'3D interpenetrated network. The structuralcharacteristics of crystalline materials are analyzed in detail. Moreover, the thermalstabilities, fluorescent activities or magnetic properties of these materials have beeninvestigated.[Zn(C4O4)0.5(OH)]n(1){[Cd(C4O4)0.5(OX)0.5(H2O)]}n(2){[Co(C4O4)(bpe)(H2O)2]}n(3){[Zn(C4O4)(4,4′-bpy)(H2O)2]·2H2O}n(4)Secondly, this thesis presents the preparation of nine crystalline materials constructedfrom a new conjugated biphenyl-pentacarboxylic acid and Co(II) under hydrothermalcondition. Crystalline materials5shows a single nodal5-connected3D acs network.Crystalline materials6displays a rare (5,6)-connected3D tcj/hc net. Crystalline materials7shows a three-dimensional supramolecular structure formed by the hydrogen-bondinteraction among zero dimensional moleculars. Crystalline materials8is two nodal(3,4)-connected dmc topology. Crystalline materials9exhibits a three nodal (3,4,4)-connected network. Crystalline materials10features a three-dimensional structureformed by the hydrogen-bond interactions among one-dimensional chains. Crystallinematerials11and12are isostructural (5,7)-connected3D networks. Crystalline materials13shows3D fsc network. Moreover, the magnetic properties for the above mentioned crystalmaterals were investigated.{[CoIII(H2O)6]1/3[CoII2(bpbc)(H2O)2]·2H2O}n(5){[Co4(Hbpbc)2(4,4′-bpy)(H2O)2]·2H2O}n(6){[Co(H4bpbc)2(2,2′-bpy)4]·H2O}n(7){[Co2(Hbpbc)(2,2′-bpy)2(H2O)]·H2O}n(8){[Co2(Hbpbc)(bix)2]·H2O}n(9){[Co(H3bpbc)(bpp)]·2H2O}n(10){[Co3(μ3-OH)(bpbc)(dps)(CH3CH2OH)]·4H2O}n(11){[Co3(μ3-OH)(bpbc)(dpa)(H2O)]·3H2O}n(12){[Co2(Hbpbc)(bib)(H2O)4](bib)0.5·3H2O}n(13)Finally, by using biphenyl-pentacarboxylic acid and Ln(NO3)3·6H2O, a series ofLn-MOFs, namely {[Ln3(bpbc)(Hbpbc)(H2O)8]·3H2O}n(Ln=Nd(14), Pr(15), Sm(16),Eu(17)) have been synthesized under solvothermal condition. Structural analysis revealthat four complexes are isomorphic and display3D4,5,7T12topological networks. Besides,the thermal stabilities, magnetic properties and fluorescent activities of these crystallinematerials have been studied.