| Salen-type ligands and analogues owing to their most versatile chelate ligands have been to a hot spot in inorganic and organometallic chemistry. Plenty of the metal complexes are utilized to a catalyst in various of nonlinear optical materials, organic reactions and metallomesogens. Some exhibit interesting in magnetic properties. Recently, salen are also utilized to one part which is a building block of supramolecular structures; and another part is sensing of chiral organic molecules. Therefore, the design and synthesis of asymmetrical Salamo-type compounds have an important significance position of Salen-type compounds. In addition, the introduction of different solvent molecules may also have an influence upon supramolecular structure in some extent.In this thesis, the first step, synthesised a diamine derivative 1, 2- dibromoethane. Second, the reaction of 3, 5- dibromo salicylaldehyde or 5-chlorosalicylaldehyde with excess 1, 2- bis(aminooxy)ethane gave a mixture containing the desired mono- oxime and a small amount of dioximes. Then, the pure monooxime was obtained after silica gel chromatographic separation of the crude product. Using the stable monooxime, we can get three kinds of unsymmetrical salamo ligands 5- nitro- 4′,6′- dibromo- 2, 2′- [ethylenediyldioxybis(nitrilomethylidyne)]diphenol(H2L1), 4- nitro- 5′- hydroxy- 2, 2′- [ethylenediyldioxybis(nitrilomethylidyne)]diphenol(H2L2), 5- methoxy- 4′- bromo- 2, 2′- [ethylenedioxybis(nitrilomethylidyne)]diphenol(H2L3).A lots of metal complexes have been designed,and then synthesized the reaction of these ligands with Co(OAc)2·4H2O, Ni(OAc)2·4H2O, Cu(OAc)2·H2O and Zn(OAc)2·2H2O, respectively. In nonaqueous solvents, the single crystals of one ligand and four transition metal complexes have been obtained by means of naturally evaporation of solvents.It is H2L3;(1) [{Ni L3(n-C5H11OH)(μ-OAc)}2Ni]·n-C5H11OH;(2) [{Ni L3(C2H5OH)(μ-OAc)}2Ni]·C2H5OH·H2O;(3) [{Ni L3(n-C3H7OH)(μ-OAc)}2Ni]·n-C3H7OH;(4) 2[{Ni L3(n-C4H9OH)(μ-OAc)}2Ni]·2n-C4H9OH·H2O. These complexes were measured by using of X-ray single crystal diffraction analysis in order to determine their composition and spatial configuration. Meanwhile, some complexes fluorescence properties were studied to explore the mechanism of photoluminescence. The crystal data:H2L3: Empirical formula, C17H17 Br N2O5, formula weight, 409.24, Triclinic, space group: P1, cell parameters: a = 10.4351(9) ?, b = 4.5807(4) ?, c = 18.2369(17) ?, β = 100.663(2)°, V = 857.85(13) ?3, Z = 2, R1 = 0.0953, w R2 = 0.2194;Complex 1: Empirical formula, C58H84Br2N4Ni3O18, formula weight, 1461.24, Triclinic, space group: P-1, cell parameters: a = 10.6568(8) ?, b = 12.4987(11) ?, c = 14.4302(13) ?, β = 75.918(2)°, V = 1673.4(2) ?3, Z = 1, R1 = 0.0654, w R2 = 0.1680;Complex 2: Empirical formula, C46H60Br2N4Ni3O18, formula weight, 1292.93 Triclinic, space group: P-1, cell parameters: a = 9.2829(8) ?, b =11.0400(9) ?, c = 14.220(1) ?, β = 84.361(2)°, V = 1338.2(2) ?3, Z = 1, R1 = 0.0525, w R2 = 0.1191;Complex 3: Empirical formula, C50H72Br2N4Ni3O20, formula weight, 1385.07, Triclinic, space group: P-1, cell parameters: a = 10.7475(9) ?, b =12.1999(11) ?, c = 12.4027(14) ?, β = 112.000(3)°, V = 1466.8(2) ?3, Z = 1, R1 = 0.1482, w R2 = 0.2186;Complex 4: Empirical formula, C54H76Br2N4Ni3O18, formula weight, 1405.14, Triclinic, space group: P-1, cell parameters: a =10.8973(11) ?, b = 12.4386(13) ?, c = 12.5175(14) ?, β = 88.596(2)°, V = 1531.7(3) ?3, Z = 1, R1 = 0.0307, w R2 = 0.1167;... |
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