Study On The Synthesis And Properties Of N - Type Ligand Sulfide And Pyridone Metal Complexes

Strategies based on the use of metal ions as nodes and organic ligands as linkers for the construction of intriguing supramolecular architectures have undergone phenomenal development. These metal organic complexes have a wide variety of structures, which was affacted by ligand, metal, anionic species, conditions, methods and so on.In the first chapter of this thesis, we introduced the classification, features, and description method of the metal organic complexe structure, firstly. The structure of the complexes is roughly divided into the four kinds:zero dimension and one dimension, two dimension and three dimension, which is not only affected by organic ligand and metal ion species, but influenced by counter anions. Under the condition of same ligand and metal, the different complexing ability of the counter ion often leads to different structure of complexes. Meanwhile, the anion…π weak interaction also play an important role in the formation of the complexes. After that, we introduced the research progress of two types of semi-rigid angular-shaped ligands: pyrazinylsulfide and pyridinylmethanone. The C-S-Cσ key rotation effect of pyrazinylsulfide (C-S-C about 100 de.) and the C-C-C σ key rotation effect of pyridinylmethanone(C-CO-C about 100 de.) make the two ligands have great similarities on the coordination model.In the second chapter of this thesis, we introduced the synthesis and characterization of pyrazinylsulfide. On the one hand, the diversity of coordination model of pyrazinesulfide with metal ions illustrates the C-S-C rotation effects. On the other hand, the differences in the strucetures of the series of complexes formed by pyrazinesulfide and Ag(Ⅰ) anion indicated the different coordination abilities of the counter ions. In addition, anion…π weak interaction among the various forces which contains hydrogen bonding, also play an important role in the formation of the complexes.In the third chapter of this thesis, we introduced the di-3-pyridinylmethanone and its one-pot method of carbonyl reduction reaction in-suit. Cadmium (II) trifluoroacetate and silver(I) pentafluoropropionate complexes of the secondary alcohol form of di-3-pyridylmethanone were produced by reduction reaction in-situ of di-3-pyridyl ketone in the present of aluminum powder and potassium fluoride via solvent-thermal synthesis. Single crystal X-ray diffraction analyses revealed that di-3-pyridinylmethanone underwent carbonyl reduction in situ to form its secondary carbinol form (3-py)2C(OH)H, a first example in the family of di-pyridyl ketone.In the forth chapter of the thesis, we introduce the asymmetric pyridine ketone which was synthesized by introducing substituent on the aromatic ring of pyridine ketone. Three Ag (Ⅰ) matal complexes of the asymmetric pyridine ketone were obtained through volatilization and diffusion method, and the structures of which was characterized by X-ray crystal structure analysis. Because of the introduction of the substituent on the aromatic ring, the asymmetric angular-shaped ligand exhibited different coordination modes compared with before.