Study Of Self-Assembly And Host-Guest Chemistry Based On Open Chain Polyether-Bridged Ligands And Salen Ligands And 1,2,4-Triazole Bridged Ligands

Inorganic-organic supermolecular complexes driven by coordination haveturnable, stable and modifiable structure. These advantages enable the supermolecularcomplexes apply in many fields, such as the small molecular separation,heterogeneous catalysis, magnetism and luminescent materials.The geometry of the ligand and coordinative ability of the atoms is the decisivefactors. In this thesis, we mainly research the open-chain polyether-bridged flexibleligands with pyridine and the chiral diamine bridged salen ligands. The coordinationchemistry based on these new ligands and transition metal ions was investigated. 36new coordination polymers were prepared and fully characterized by IR, elementalanalysis, X-ray single-crystal diffraction, TGA, luminescent property. We alsoresearch the effective recognization of CH₂Cl₂of macrocycles.MOFs have many advantages,such as various structure, size can be adjusted andhigh purity, which provide the conditions for scientists to study the adsorption,separation and sensor detection of small molecules. In this paper we research theapplication of Cd（Ⅱ）-MOF which have been reported in detecting the Benzoquinon ineaqueous solution. We also research the application of Cd（Ⅱ）-MOF in reversiblesorption-desorption and separation about Hydroquinone and Benzoquinone.I. A series of open-chain polyether-bridged flexible ligands with pyridinehave been designed and synthesized. The self-assembly of the ligands andtransition metal ions Zn（Ⅱ）、Hg（Ⅱ）、Cd（Ⅱ）、Co（Ⅱ）、Mn（Ⅱ）、Cu（Ⅱ） hasbeen investigate. 30 new coordination polymer were synthesized basedon them. We also discussed the affection of the coordination modes of theligands and the template of the solvent. We mainly investigate theadsorption and desorption properties of the coordination polymer[Zn（L₂）₂]Cl4·₂（CH₂Cl₂） （1）, with the significant change of theluminescent property. The desolvation compounds [Zn（L₂）₂]Cl4（₂） candistinguish CH₂Cl₂among the mixture of the CH₂Cl₂,CHCl3,CCl4.Ⅱ. we introduc the pyridine and carboxylic into the chiral diamine ligands to synthesize two kinds of salen ligands. The coordination chemistry basedon pyridine-bridged chiral Salen ligands and Ni（OAc）₂has beeninvestigated, two novel Ni-Salen compouds [NiL9]·（CH₃OH） （31） and[NiL10]·（CH₃OH） （3₂）, the righthanded rotation Ni-Salen compound 3₂further assemble with HgI₂to get the coordination polymer{ [Hg（NiL10）I₂]·（CH₃OH） （H₂O） }n（33）. The chiral Salen ligands withcarboxylic assembled with Zn（Ⅱ） get two novel compounds Zn-Salen[Zn4L114]·5（CH₃OH） （34） and [Zn4L1₂4]·5（CH₃OH） （35）.Ⅲ. we research the application of Cd（Ⅱ）-MOF which have been reported indetecting the Benzoquinon in eaqueous solution. The chiral Cd（Ⅱ）-MOF（[Cd（L6）₂（ClO4）₂]·H₂O） based on 1, ₂, 4-triazole bridging ligand havenanoscale channel. The results of the study show that, in 55.0 mg/L, 1.0mg/L, 0.₂ mg/L these three kind of concentration of the aqueous solutionof Benzoquinon, Cd（Ⅱ）-MOF can quickly detecte the existence ofBenzoquinon. We have explored the fluorescent sensor responsemechanism of Cd（Ⅱ）-MOF, the result indicates that it is the object of freeradicals caused the fluorescent quenches of the system. This paper alsostudies the application of Cd（Ⅱ）-MOF in reversible sorption-desorptionand separation about Hydroquinone and Benzoquinone, usinghigh-performance liquid chromatography （HPLC） adsorption to detectthe relative content of Hydroquinone and Benzoquinone.The results show that the above open chain polyether-bridged flexible ligandsand chiral Salen organic ligands can bind transition metals to get new supramolecularcomplexes. The new supramolecular complexes can be used to synthesis separationand catalytic materials. Cd（Ⅱ）-MOF also can be used to detecte the existence ofBenzoquinon and separate the Hydroquinone and Benzoquinone. The study expandsthe application of MOFs as small molecular sensors and separation material.