Self-Assembly Chemistry Based On Pyridine-ended Bent Ligands And Research About Photodimerization On MOFs

Recently, supramolecular chemistry, which is mainly research on the molecularassembly, structure and functions, has gained much attentions. The design andsynthesis of ligands is always the main point for supramolecular chemistry. Throughassemble of inorganic metal salts and organic ligands, we get a batch of novelfunctional materials with excellent properties. In this thesis, we have synthesized aseries of asymmetric rigid ligands, flexible ligand bridged by sulfur ether. We alsoexplored the self-assembly of these ligands and inorganic metal ligands underhydrothermal and solvent conditions. We totally prepare 22 new coordinationpolymers and fully characterize by IR, elemental analysis, X-ray single-crystaldiffraction and powdered X-ray diffraction.1. We have synthesized three novel symmetrical Schiff-base ligands withphenyl-pyridine, and exploited their self-assembly coordination chemistry withZn(Ⅱ), Cd(Ⅱ), Mn(Ⅱ) ions. Five new coordination polymers were synthesized basedon them and their crystal structure were discussed in detail. Compared with theexisting Schiff-base ligands, the extended ligands we have synthesized can expandthe size of coordination polymer effectively.2. We have synthesized a series of asymmetric rigid pyridine-based ligands, andexploit the self-assembly of these ligands, terephthalic acid, and Cd(Ⅱ), Hg(Ⅱ) ions.Finally we get seven novel metal-organic frameworks.3. We have synthesized two coordination polymer, which characterized composedby 2-hydroxyquinoline-4-carboxylic acid, Mn(OAc)2, 4, 4’-bipyridine and 4,4’-azobispyridine (azpy), to complete the research for one-DimensionalCoordination Polymer-Templated [2+2] Photodimerization Irradiated by SolarRadiation. We take {Zn(bpa)n} as example to research the conditions for the dimersto open and close.4. Twoβ-diketone with 1, 3, 4-oxdiazole ligand have been synthesized to researchthe coordination chemistry with the Cu(Ⅱ) and Co(Ⅱ), then get two novelcoordination polymers. 5. We research the self-assembly of bis(3-pyridylmethyl)sulfide and Ag(I) salts todiscuss the affect of the solvent, molar ratios between the ligand and metal,temperature and anions for coordination chemistry.6. We synthesized a series of sulfur ether bridged flexible ligands to complete theresearch of flexible ligands of our research group. We also exploit the luminescentproperties of some ligands.In this thesis, we have demonstrated that the ligands we have synthesized canmake supermolecules and our work can be the foundation of the coordinationchemistry of these ligands. We also exploit the influence of the solvent, the molarratio, the temperature and the anions for the self-assembly. We have completed theresearch for one-dimensional coordination polymer templated [2+2]photodimerization irradiated by solar radiation.