| In this thesis, eight new bipyridine-like or terpyridine-like compounds in two series were synthesized and charactered by Elemental analyses, IR spectra, 'HNMR, Thermal analyses etc. With these compounds, 12 coordination polymers were obtained and their crystal structures and properties were studied.1. In the presence of potassium carbonate, a, a'-dichlor-p-xylene reacted with Benzimidazole to give 1,4-bis(l-benzimidazolylmethyl)benzene(Li) in high yield. When a,a'-dichlor-p-xylene reacted with 2,4-pentanedione, 1,4-bis[2,5-dioxy- 3-pentylmethyl] benzene (L2) was obtained. The LI reacted further with hydroxylamine or hydrazine to give l,4-bis[4-(3,5-dimethyl-l-isoxazolyl)methyl] benzene(L3) and 1,4-bis[4-(3,5-dimethyl-1 -pyrazolyl)methyl] benzene(L4), respectively. Diethyl-2,5-diacetylsuccinate reacted with hydrazine to give (3,3-dimethyl)-(5,5-di)-4,4-dipyrazole(L5).The coordination properties of the above compounds were studied. Three novel coordination polymers of LI with metal ions, [Cu(II)(NO3)2(Li)]n (1), [Mn(II)Cl2(Li)2]m (2) and [Cd(II)Cl2(Li)2]m (3) were obtained. X-ray single crystal diffraction analysis showes that polymer 1 exhibits a distorted tetrahedron, in its structure the mental atom is coordinated by two nitrogen atoms from two LI and two oxygen atoms from two NOs" groups. Each Cu(II)(NO3)2 unit is bridged by LI to form a zigzag chain structure; Polymer 2 and 3 are two-dimensional network. The coordination environment of Mn(II) and Cd(II) are a distorted octahedron.In the presence of hydrochloric acid, 1,4-bis(l-benzimidazolylmethyl) -benzene(Li) reacted with zinc chloride to give a new supramolecular complex of [H2(Li)ZnCLi]-H2O. The crystal structure showes that the zinc(II) atom is coordinated by four chloride ions and connected with protonated LI and H2O through H-bonding, thus forming a 3-d2. In the presence of triethylamine containing about 11% diethylamine , 2,4-Bis(3,5-dimethyl-1-pyrazolyl)-6-diethylamino-1,3,5-triazine(L6) was obtained by the reacted of 2,4,6-trichloro-l,3,5-triazine with 3,5-dimethylpyrazole. But in the presence of potassium carbonate, 2,4,6-trichloro-l,3,5-triazine reacted with 3,5-dimethylpyrazole to give 2,4,6-tris(3,5-dimethyl-l-pyrazolyl)-l,3,5-triazine(L8). When 2,4,6-trichloro-l,3,5 -triazine reacted with 2,4-pentanedione in the presence of potassium carbonate, 2,4,6-tri(2,5-dioxy-3-pentylmernyl)-1,3,5-triazine(L7) was obtained. The complexes of L6 with Y, La, Ce, Pr, Nd and Eu were obtained. The structures of these complexes, [YL6(NO3)3] (1) and [LnL6(NO3)3(H2O)]L6 (Ln=La, 2; Ce, 3; Pr, 4; Nd, 5; Eu, 6), have been determined by x-ray crystal structural analysis.The structures of the five lanthanoid complexes are isomorphous and isostructural, which are different from the crystal structure of the Yttrium complex [YL6(NO3)3]. Thelatter shows a nine coordinate metal center but the crystal structure of the lanthanoid complexes [LnL6(NO3)3(H2O)]L6 are ten-coordinate metal center. The TC-TC stacking and hydrogen bonding between the coordinated and uncoordinated Le molecules sensitized the Ln luminescence. The thermal behavior of the ligand and its complexes are also discussed. The complexes of Co(1) and Mn(2) with 2,4-bis(3,5-dimethylpyrazol-1-yl)-6-diethylin-1,3,5-triazine were synthesized and and studied their structure.3. The luminescence spectra of the powdered solid complexes were obtained for at room temperature. The results show that only Eu complex have the properties of luminescence. Study of the luminescence spectra shows that the special molecular chelating structure of terpyridine and the terpyridine-like compounds can enhance the luminescence of lanthanide substantially.All the compounds and complexes were not reported. |
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