Study On Synthesis,Crystal Structures And Property Of New Schiff-base Complexes

The Schiff base usually is a kind of organic compound, which contains amino or alkane the amino, and formed by lively carbonyl and amino. Because of the lone pair electrons of N atom of C=N about the structure of the Schiff base, that can form stable complexes with transition metals, which has become one of the hot research of chemistry the coordination. Because the metal complexes of Schiff base have unique structures and excellent properties, so they have a very important significance in many fields, such as analytical chemistry, biological catalysis, medicine and pesticide, molecular assembly, molecular magnetism and antitumor, supramolecular chemistry, material science, and so on. In recent years, the studies of amino coumarin compounds and the metal complexes of Schiff base are gradually active. The synthesis of these compounds are flexible and simple, and can form the stable metal complexes with most metal ions. They have a wide application value in anticancer, antibacterial, antitumor medicine, and are focus on catalysis, optical physical materials, surface chemistry, and so many research fields. Because of the coumarin compounds with the good fluorescent, and with tunable emission, visible light excitation and emission, high fluorescence quantum yield, two-photon effect, large Stokes shift, good biological compatible and stable chemical properties.In order to obtain some functional coumarin compounds or metal complexes, the electron rich groups are added on the coumarin ring, which can not only enhance the coordination ability of transition metal ions to form the metal complexes with good fluorescent properties, but also can control the excitation and emission wavelengths to identify some transition metal ion. This paper firstly added-NH₂ onto the position 6 of coumarin ring, then reacted with salicylaldehyde compounds and obtained two kinds of 6-amino coumarin Schiff base compounds HL1 and HL₂?HL¹ = 6-[?4-Diethylamino-2-hydroxy-benzylidene?-amino]-chromen-2-one, HL² = 6-[2-Hydroxy-4-methoxy-benzylidene?-amino]-chromen-2-one). Through the spectral properties of experimental test, found that ligand HL¹ can recognite the Hg²⁺ in DMF solution with UV; Schiff ligand HL² can be used as fluorescent probe. Not only has the fluorescence and excellent selectivity for Zn²⁺ ion in DMSO, and has high sensitivity. At the same time, as ligands HL¹ and HL² reacted with transition metal ions, and got the Zn???, Co??? complexes and determined their crystal structures, discussed the matter of hydrogen bonds,stacking and other weak interactions, and studied their fluorescence properties. In addition, a kind of 3-amino coumarin Schiff base compound H₂L³?4-Hydroxy-3-[2-Hydroxy-4-methoxybenzylidene?-amino]-chromen-2-one) was synthetized, and reacted with Zn???, Ni???, Cr??? and Co??? and other transition metals, obtained single crystals of these transition metal complexes, and the crystal structures, chemical composition and spatial structures have been determined, discussed their supramolecular interactions.The main crystal data are listed as following:Zinc??? Complex [Zn?L¹?₂]: Empirical formula, C₄₀H₃₈ZnN₄O₆, Formula weight, 734.10, Monoclinic, space group: C2/c, Unit call dimensions: a = 25.715?4? ?, b = 9.8320?9? ?, c = 13.796?2? ?, ? = 90.003?1?°, ? = 93.88?1?°, ? = 90.02?1?°, Z = 4, V = 1973.4?3? ?3, R1 = 0.0863, wR₂ = 0.2551;Cobalt??? Complex [Co?L1?2]: Empirical formula, C₄₀H₃₈CoN₄O₆, Formula weight, 729.67, Monoclinic, space group: C2/c, Unit call dimensions: a = 25.848?2? ?, b = 9.7537?5? ?, c =13.830?1? ?, ? = 90.00°, ? = 93.760?7?°, ? = 90.00°, Z = 4, V = 3479.3?4? ?3, R1 = 0.077, wR₂ = 0.223;Cobalt??? Complex [Co?L2?2]: Empirical formula, C₃₄H₂₄CoN₂O₈, Formula weight, 647.48, Triclinic, space group: P, Unit call dimensions: a = 9.31?7? ?, b = 12.31?6? ?, c = 13.02?4? ?, ? = 83.7?4?°, ? =75.8?6?°, ? = 82.4?6?°, Z = 2, V = 1430?1? ?3, R1 = 0.0703, wR₂ = 0.1777;Zinc??? Complex [Zn₂?L³?₂·?CH₃OH?₄]: Empirical formula, C₃₈H₃₈N₂O₁₄Zn₂, Formula weight, 877.44, Monoclinic, space group: P21/n, Unit call dimensions: a = 9.6906?6? ?, b = 7.9055?5? ?, c = 24.0501?18? ?, ? = 90.00 °, ? = 99.878?7? °, ? = 90.00 °, Z = 4, V = 1815.1?2? ?3, R1 = 0.0474, wR₂ = 0.1143;Cobalt??? Complex [Co₂?L³?₂·?CH₃OH?₄]: Empirical formula, C₃₈H₃₈N₂O₁₄Co₂, Formula weight, 864.56, Monoclinic, space group: P21/n, Unit call dimensions: a = 9.7459?5? ?, b = 7.9026?7? ?, c = 24.062?1? ?, ? = 90.00°, ? = 100.260?9?°, ? = 9 0.00 °, Z = 4, V = 1823.6?2?, R1 = 0.058, wR₂ = 0.120;Chrome??? Complex [Cr₂?L³?₂·?CH₃O?₂·?CH₃OH?₂]: Empirical formula, C₃₈H₃₆N₂O₁₄Cr₂, Formula weight, 848.68, Triclinic, space group: P, Unit call dimensions: a = 8.286?1? ?, b = 8.286?1? ?, c =12.150?1? ?, ? =113.42?1?°, ? = 93.32?1?°, ? = 107.85?1? °, Z = 2, V = 897.7?2? ?3, R1 = 0.045, wR₂ = 0.111;Nickel??? Complex [Ni₂?L³?₂·?CH₃OH?₄]: Empirical formula, C₃₈H₃₈N₂O₁₄Ni₂, Formula weight, 864.12, Monoclinic, space group: P21/n, Unit call dimensions: a = 9.669?1? ?, b = 7.915?1? ?, c = 23.981?1? ?, ? = 90.000°, ? = 99.956?9?°, ? = 90.000 °, Z = 4, V = 1807.9?3? ?3, R1 = 0.088, wR₂ = 0.184.