非对称结构的Salen型镍、铜、锰配合物的合成及性质

本文设计合成了两种新型Salen配体H2L1(N-苯基-N-(2-羟基-5-甲基苯基)-N′-(2,5-二羟基苯基)-4,5-二甲氧基邻苯二胺)和H2L2(N-苯基-N-(2-羟基-5-甲基苯基)-N′-(2-羟基-3,5二叔丁基苯基)-4,5-二甲氧基邻苯二胺)及相应的过渡金属配合物MLn(M=Ni、Cu、Mn;n=1、2)。分别采用核磁、质谱、元素分析、红外光谱和紫外-可见光谱对目标化合物进行了表征。研究了两种配体及其金属配合物的荧光性质,探讨了配体结构及中心金属离子对其荧光性质的影响。研究发现,由于氢键的作用使得配体H2L1的荧光强度远低于H2L2;中心金属离子的嵌入对H2L2的荧光强度有明显的猝灭作用。用循环伏安法研究了配体及其金属配合物的电化学氧化还原性质,并测定了配体及其金属配合物溶液的电导率、摩尔电导率。结果表明,镍、铜、锰配合物的氧化还原过程均为准可逆的单电子过程;且在所研究的配体和配合物中,金属锰配合物溶液的导电能力较强。

Synthesis and Properties of Salen-Type Ni, Cu, Mn Complexes with Asymmetrical Structure

Two Salen-type ligands H2L1(N-phenyl-N-(2-hydroxyl -5-methylphenyl)-N′-(2,5-dihydroxyphenyl)-4,5-dimethoxyl-o-phenyldiamine),H2L2(N-phenyl-N-(2-hydroxy-5-methylphenyl)-N′-(2-hydroxy-3,5-di-tert-butylphen-yl)-4,5-dimethoxyl-o-phenyldiamine) and their metal complexes MLn(M=Ni,Cu,Mn;n=1,2) were synthesized and characterized by 1H NMR,ESI-MS,elemental analysis,FTIR,UV-Vis spectra.The fluorescence properties of H2L1,H2L2 and their metal complexes have been studied.The influences of the ligands structures and central metal ions were also investigated.Because of the effect of the hydrogen bonds,the fluorescence intensity of H2L1 was far lower than that of H2L2.However,the embedded central ions of Ni(Ⅱ),Cu(Ⅱ) and Mn(Ⅱ) showed the quenching effect on fluorescence of H2L2.The electrochemical redox properties of H2L1,H2L2 and their metal complexes were investigated by cyclic voltammetry.In addition,the solution conduction properties of the research system were explored through the determination of conductivity and the molar conductivity.As a result,the oxidation-reduction processes of Ni(Ⅱ),Cu(Ⅱ) and Mn(Ⅱ) complexes were quasi reversible single-electron processes,whereas the embedded Mn(Ⅱ) made the conductive ability of the Mn(Ⅱ) complex solution enhance greatly.