| Salen-type ligands and their derivatives have an important position in the field of modern coordination chemistry as a kind of tetradentate ligands. they have relatively strong coordination ability to transition metal ions and applied to the synthesis of transition metal complexes,capable of forming stable metal complexes.They have unique properties and various structure,for example, they can be used as models of reaction centers of metalloenzymes, catalysts for organic reactions,nonlinear optical materials, and they can also be applied to the fields such as analytical chemistry,magnetism and biochemistry and so on.But the Salen-type compounds with asymmetrical structure are relatively rare.Electronic and steric effect of the ligands may be effectively controlled by introduction of different substituents into the two benzene rings. The asymmetrical configuration can afford more opportunities of a greater structural variation and infinite coordination polymers,which could be expected to lead to novel characteristics and better enantioselectivities when compared with their symmetrical counterparts.Therefore, the design and synthesis of asymmetrical Salamo-type compounds have the important significance, which are as a kind of important Salen-type compounds. In addition,in order to effectively control the supramolecular self-assembly, the introduction of different solvent molecules may also have an influence up on supramolecular structure to some extent.So can we do some further research on the basis of a variety of new complexes, such as the properties of light, electricity, magnetic,catalytic and applicatial prospects of complexes in medicine, biochemistry and some functional materials.In this paper,four asymmetric Salamo-type ligands have been designed and synthesized based on1,2-bis(aminooxy)ethane and different salicylaldehyde derivatives with4-(N,N-diethylamine)-2-hydroxybenzaldehyde.By using the stable monooxime, we can obtain seven kinds unsymmetrical salen ligands:5-(N,N-diethylamine)-5’-methoxy-2,2’-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol(H2L1),5-(N,N-diethylamine)-6’-chloro-2,2’-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol(H2L2)5-(N,N-diethylamine)-4’,6’-dibromo-2,2’-[ethylenediyldioxybis(nitrilomethylidyne)]diphenol(H2L2),which were characterized by IR,UV-Vis, fluorescence spectra and a series of physical and chemical analysis methods.Using these new ligands and Co(II) Zn(II)and Ni(II) acetatein an organic solvent, we synthesized a series of new Salamo Co(II) Zn(II)and Ni(II) complexes. In different solvent systems, through natural evaporation of the solvent or solvent thermal method, we obtained seven novel Co(II) 、 Zn(II)and Ni(II) complexes.And then we used X- ray diffraction method to determine the crystal structure of the chemical composition and space.Corresponding crystallographic data are listed as follows:Complex 1: Empirical formula: C50H72Co3N6O18, formula weight: 1221.93,monoclinic,space group: P 21/n, cell parameters: a = 12.5827(14)?, b = 16.3724(15)?, c =14.1058(10) ?, α= 90°, β = 99.456(8)°, γ = 90°, Z = 2, V = 2866.4(5) ?3, R1 = 0.0698, wR2 =0.1932;Complex 2: Empirical formula: C46H56N6O14Zn3, formula weight: 1113.14, monoclinic,space group: C 2/c, cell parameters: a = 10.6703(7) ?, b = 27.091(4) ?, c = 17.9132(16) ?,α=90°, β = 96.246(8)°, γ = 90°, Z = 4, V = 5147.4(10) ?3, R1 = 0.0647, wR2 = 0.1865;Complex 3: Empirical formula: C58H86N8Ni3O18, formula weight: 1359.42, Triclinic,space group: P-1, cell parameters: a = 11.4561(8) ?, b = 13.1859(8) ?, c = 13.5063(11) ?, α= 109.620(7)°, β = 101.234(7)°, γ = 114.469(6)°, Z = 1, V = 1611.1(3) ?3, R1 = 0.0518, wR2=0.1315;Complex 4: Empirical formula: C44H49Cl2Co3N6O12, formula weight: 1101.59, Triclinic,space group: P-1, cell parameters: a = 9.7415(9) ?, b = 13.6440(14) ?, c = 20.277(3) ?, α =72.807(10)°, β = 83.019(9)°, γ = 72.246(9)°, Z = 2, V = 2450.6(5) ?3, R1 = 0.0700, wR2 =0.1505;Complex 5: Empirical formula: C44H50Cl2N6O12Zn3, formula weight: 1121.97,Triclinic,space group: P-1, cell parameters: a = 9.7387(8) ?, b = 13.7034(12) ?, c = 20.2498(16) ?, α= 72.539(8)°, β = 82.872(7)°, γ = 72.157(8)°, Z =2,V = 2452.3(4) ?3, R1 = 0.0604, wR2 =0.1375;Complex 6: Empirical formula: C44H58Cl2N6Ni3O16, formula weight: 1173.94,monoclinic,space group: P 21, cell parameters: a = 9.4461(4) ?, b = 18.8477(10) ?, c =14.7064(6) ?, α = 90°, β = 93.952(4)°, γ = 90°, Z = 2, V = 2612.1(2)?3, R1 = 0.0636, wR2 =0.1391;Complex 7: Empirical formula: C43H48Br4Co2N6O9, formula weight: 1230.34, Triclinic,space group: P-1, cell parameters: a = 11.9298(7) ?, b = 12.8850(9) ?, c = 17.5241(11) ?, α=84.854(6)°, β = 85.181(5)°, γ = 65.796(6)°, Z = 2, V = 2443.7(3) ?3, R1 = 0.0556, wR2 =0.1053;... |
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