| This thesis designed and synthesized a series of metal-organic framework (MOFs) which based on the reaction between the polyfunctional organic ligands and varies of metals. By hydrothermal and volatilization methods I obtained lots of novel met-al-organic frameworks from one-dimensional to three-dimensional structures. The crystal structures were determined by X-ray single crystal diffraction. In addition, through the study in infrared spectroscopy, thermal gravimetric analysis, X-ray powd-er diffraction analyzer (XRD), UV fluorescence spectroscopy, scanning electron mi-croscopy instrument, I learnt and studied more about the propotities of these MOFs.In the second chapter of this thesis, we designed and syntheses four new poly-functional groups organic ligands:namely,5-(4-carboxybenzamido)isophthalic acid (H3L1),9,9’-(9-oxo-9H-fluorene-2,7-diyl)bis(9H-carbazole-3,6-dicarboxylic acid)(H4L2), tetramethyl5,5’-(9-oxo-9H-fluorene-2,7-diyl)diisophthalate (H4L3) and5-((4-carboxyphenyl)ethynyl)isophthalic acid (H3L4).In the third chapter of this thesis, we mainly discussed five new metal-organic frameworks with5-(4-carboxybenzoylamino)-isophthalic acid (H3L1), namely,[Cd9(L,)6(DMA)6]-4DMA (1),[Cd3(L1)2(H2O)9]·4H2O (2),[La(L1)(H2O)4]·2H2O (3),[Ce(LJ)(H2O)4]·H2O (4) and [Tb(HL1)(H2L,)(H2O)3]·5H2O (5)(DMA N,N-dimethylacetamide), have been synthesized. Complex1shows a three-dimensional architecture generated from linkage of Cd-O chains via L3-ligands. Minor variations in synthetic conditions of1afforded2, which features an interesting2D'3D catenation architecture containing helical chains. Complexes3and4are isostructural and each feature a two-dimensional architecture constructed from the linkage of L3-with Ln3+. Complex5displays a chain-like structure, of which the most interesting feature is the existence of free carboxylic acid (-COOH) group which may confer unique functionality.5-(4-carboxybenzoylamino)-isophthalic acid (H3L1) with Zn(NO3)2·6H2O to generate a novel porous MOF under solvothermal condition, namely,[Zn3(L1)2(DMF)2]-2DMF (6), which undergoes a remarkable crys-tal-to-crystal transformation to afford [Cu3(L])2(DMF)2]·2DMF(7) by immersed6 into the DMF/H2O solution of Cu(NO3)2·3H2O and left undisturbed at ambient tem-perature for five days.In the fourth chapter of this thesis, we focused on:how the5-(4-carboxy-ben-zoylamino)-isophthalic acid (H3L1),4,4-bipyridine (L5) with metal Zn build the MOFs; how5-(4-carboxy-benzoylamino)-isophthalic acid (H3L1),1,2-bis(4-py-ridyl)-2-triazene (L6) with the metals Co/Ni build MOFs; how5-(4-carboxy-benzoy-lamino)-isophthalic acid (H3L1),1,2-bis(4-pyridyl) ethylene (L7) and metals Co/Cd/Zn build MOFs.In the fifth chapter of this thesis, we used5-(4-carboxyphenyl) ethy-nyl-isophthalic acid (H3L4) with metal Cd build a metal-organic framework, there is a rare Cd-O trinuclear cluster in this structure. While in the sixth chapter, we tried to introduce-NH2,-OH,-NO2,-COOH,-NHCO-,-C=C-functional groups into the channel during the synthesis process. Several MOFs were designed and synthesized based on the ligands containing-NH2,-OH,-C=C-type functional groups, we ex-pected to modify the structure of these MOFs in the later research. It is well known that certain functional groups in the channel can become potential catalytic sites in some organic reactions. |
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