| Salen-type bisoxime compounds and their derivatives belongs to the category of the schiff base, are a class of tetradentate ligand which have large conjugated system. The presence of N2O2 structure in such ligands can form stable complexes with most metal ions. So far, Salen-type bisoxime complexes have been widely used in light, electricity, magnetic, catalysis, medicine, biochemistry and functional materials. Design and synthesis of new compounds and their metal complexes, research the structure, properties and applications in new areas are all have great significance and value.In this thesis, two kinds of diamines, 1,2-bis(aminooxy)ethane and 1,3-bis(aminooxy) propane are synthesized at first. In the second place, eight new ligands are synthesized by next precursors: 2,6-dihydroxyacetophenone, 2-hydroxy-3-aminoacetophenone, 2-hydroxy-1-aldehyde, 3-ethoxy-salicylaldehyde, 5-bromosalicylaldehyde, 3,5-dichloro-salicylaldehyde, 3,5-dibromosalicylaldehyde, 5-chlorosalicylaldehyde, and 3-hydroxysalicylaldehyde. Then two ligand crystals and 5 crystals of transition metal: Zn(II) and Co(II) complexes are determined. The ligands of H4L1, H4L2, H6L3, H2L4, H2L5, H2L6, H3L7, H3L8 and their complexes are characterized by point melting, elemental analysis, solubility measurement, IR, UV, fluorescence spectra and differential thermal methods. Crystal structure and chemical composition of H2L4 and H2L5 ligands, Co(II) complex of H2L6, Zn(II) complexes of H3L7, Co(II) complexes of H3L8 are determined by X-ray diffraction method. At last, the symmetry, spatial arrangement, accumulation of these crystals and solvent effect of some complexes are analyzed and discussed.A series of Salen-type bisoxime complexes of Co(II) and Zn(II) are synthesized in organic solvent. Single crystal of two ligands, five Co(II) and Zn(II) complexes: H2L4, H2L5, [Co(L6)(H2O)2](1), [{Zn(L7)(μ-OAc)Zn(n-Pr OH)}2](2), [{Zn(L7)(μ-OAc)Zn(H2O)}2](3), [{Co(L8)(i-Pr OH)}2Co(H2O)]?2CH3CN(4), [{Co(L8)(μ-OAc)Co(Me OH)2}2]?2CH3COCH3(5) are obtained by natural evaporation of the solvent or solvent thermal method in various solvent systems. Crystal structure, chemical composition and space group are determined by using X-ray diffraction method. Corresponding crystallographic data are listed as follows:H2L4: empirical formula: C19H15NO3, Mr: 305.32, monoclinic, space group: P(2)1/n, cell parameters: a = 9.1811(4) ?, b = 16.0396(6) ?, c = 10.1330(5) ?, α = 90°, β = 98.640(5)°, γ = 90°, Z = 4, V = 1475.27(11) ?3, R1 = 0.0539, w R2 = 0.1373;H2L5: empirical formula: C18H19 Br N2O5, Mr: 423.26, triclinic, space group: P-1,cell parameters: a = 9.0429(7) ?, b = 9.5752(11) ?, c = 11.8422(15) ?, α = 70.954(11)°, β = 84.794(8)°, γ = 72.691(8)°, Z = 2, V = 925.33(18) ?3, R1 = 0.0511, w R2 = 0.0876;Complex 1: empirical formula: C16H14Br2Cl2 Co N2O6, Mr: 619.94, monoclinic, space group: P(2)1/c, cell parameters: a = 24.8201(9) ?, b = 10.1475(4) ?, c = 7.8671(3) ?, α = 90°, β = 91.459(3)°, γ = 90°, Z = 4, V = 1980.77(13) ?3, R1 = 0.0480, w R2 = 0.0890;Complex 2: empirical formula: C42H46Cl2N4O16Zn4, Mr: 1195.21, triclinic, space group: P-1, cell parameters: a = 9.067(1) ?, b = 11.7201(13) ?, c = 12.4367(14) ?, α = 91.649(9)°, β= 108.557(10)°, γ = 104.506(10)°, Z = 1, V = 1204.4(2) ?3, R1 = 0.0441, w R2 = 0.1167;Complex 3: empirical formula: C36H34Cl2N4O16Zn4, Mr: 555.53, triclinic, space group: P-1, cell parameters: a = 9.0742(6) ?, b = 11.8225(5) ?, c = 12.4182(8) ?, α = 90.746(4)°, β= 109.134(6)°, γ = 104.399(5)°, Z = 2, V = 1212.56(12) ?3, R1 = 0.0572, w R2 = 0.1996;Complex 4: empirical formula: C46H58Co3N6O15, Mr: 1111.77, monoclinic, space group: c2/c, cell parameters: a = 21.966(4) ?, b = 10.1801(8) ?, c = 23.081(3) ?, α = 90°, β = 97.023(10)°, γ = 90°, Z = 1, V = 5122.6(11) ?3, R1 = 0.0679, w R2 = 0.1025;Complex 5: empirical formula: C25H34Co2N2O11, Mr: 656.40, triclinic, space group: P-1, cell parameters: a = 9.8007(9) ?, b = 12.2530(7) ?, c =12.5487(9) ?, α = 73.575(6)°, β = 87.115(6)°, γ = 85.465(6)°, Z = 2, V = 1440.30(18) ?3, R1 = 0.0586, w R2 = 0.1350. |
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