Study On Syntheses, Crystal Structures And Properties Of Transition Metal Schiff Base Complexes

The Schiff base compounds and their metal complexes have attracted much attention from chemists due to their various structures and novel properties. And the Schiff base compounds, which are prepared by the condensation of aldehyde or ketone with amines or hydrazines, containing the C=N group. The N atom in the C=N group offers a pair of lone pair electrons to the metal ion. The complexes with the ligand containing the C=N group can be applied to analytical chemistry, biological medicine, pesticide, molecular assembly, material science, magnetic properties, some of them have the supramolecular structures, etc.In this dissertation, we synthesized four compounds: 1-（4-{[2-hydroxy-1-naphthalde hyde]amino}phenyl）ethanone（HL¹）, 1-（4-{[3,5-chloro-2-hydroxybenzylidene]amino}pheny l）ethanone（HL²）, 4-hydroxy-3-[（3-hydroxy-pyridin-2-ylimino）-methyl]-chromen-2-one（H L³） and 4-[（3,5-dibromo-2-hydroxy-benzylidene）-amino]-pyridin-3-ol（HL⁴）.A series of transition metal complexes [Cu（L¹）₂]（1）, [Ni（L¹）₂]（2）, [Mn4（L²’）₂（μ3-OMe）₂（μ2-OMe）₂（MeOH）₂]（3）, [Ni2（L³）₂（DMF）₂]（4） and [Zn2（L⁴）₂（H₂O）₂]·2DMF（5） have been synthesized by the reaction of ligands with copper（II） acetate monohydrate,nickel（II） acetate tetrahydrate, manganese（II） acetate dihydrate and zinc（II） acetate dihydrate. The structures of those complexes have been determined by X-ray crystal diffraction. Simultaneously, the supramolecular structures of transition metal complexes were studied in detail. The main crystal data are listed as follows:Complex 1: empirical formula C₅₂H₄₂ Cu N₄O₄; Formula weight, 850.44; Monoclinic, space group: I2/c, cell parameters: a = 21.8573（13） ?, b = 5.8605（4） ?, c = 33.683（2） ?, α = 90.00°, β = 97.428（5）°, γ = 90.00°, Z = 4, V = 4278.4（5） ?³, R₁ = 0.0554, wR₂ = 0.1042;Complex 2: empirical formula C₅₂H₄₂NiN₄O₄; Formula weight, 845.60, Triclinic, space group: P1, cell parameters: a = 5.6602（6） ?, b = 10.585（2） ?, c = 18.053（3） ?, α = 76.312（17）°, β = 96.1620（10）°, γ = 78.818（13）°, Z = 1, V = 1030.3（3） ?³, R₁ = 0.0866, wR₂ = 0.1353;Complex 3: empirical formula C₄₀H₄₀Cl₈Mn₄O₁₆; Formula weight, 1280.08, Triclinic, space group: P 1, cell parameters: a = 9.3045（13） ?, b = 11.792（3） ?, c = 12.408（3） ?, α =70.12（2）°, β = 95.7650（10）°, γ = 80.928（15）°, Z = 1, V = 1235.1（5） ?³, R₁ = 0.0823, wR₂ = 0.1922;Complex 4: Empirical formula, C₁₈H₁₅N₃NiO₅, Formula weight, 412.04, Monoclinic, space group: P21/c, Unit call dimensions: a = 9.9121（4） ?, b = 14.1192（6） ?, c = 12.4016（5） ?, α = 90°, β = 102.395（5）°, γ = 90°, Z = 4, V = 1695.16（13） ?³, R₁ = 0.0361, wR₂ = 0.0815;Complex 5: Empirical formula, C₁₂H₈Br₂N₂O₃Zn·C₃H₇NO, Formula weight, 526.49, Monoclinic, space group: P21/c, Unit call dimensions: a = 11.5966（6） ?, b = 13.9483（4）?, c = 11.3506（6） ?, α = 90°, β = 105.547（5）°, γ = 90°, Z = 4, V = 1768.82（14） ?³, R₁ = 0.0533, wR₂ = 0.1330.