Salen型化合物的合成、表征及性质

doi:10.3866/PKU.WHXB201111251

物理化学学报 >> 2012, Vol. 28 >> Issue (02): 265-272.doi: 10.3866/PKU.WHXB201111251

Salen型化合物的合成、表征及性质

刘佳, 郭莉芹, 张晓红, 阮文娟, 朱志昂

南开大学化学学院, 天津 300071

收稿日期:2011-09-08 修回日期:2011-11-21 发布日期:2012-01-11
通讯作者: 阮文娟 E-mail:wjruan@nankai.edu.cn
基金资助:
国家自然科学基金(20671053)资助项目

Synthesis, Characterization and Properties of Salen-Type Complexes

LIU Jia, GUO Li-Qin, ZHANG Xiao-Hong, RUAN Wen-Juan, ZHU Zhi-Ang

College of Chemistry, Nankai University, Tianjin 300071, P. R. China

Received:2011-09-08 Revised:2011-11-21 Published:2012-01-11
Contact: RUAN Wen-Juan E-mail:wjruan@nankai.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (20671053).

摘要/Abstract

摘要： 设计合成了两种新型Salen 配体H₂L¹ (N,N'-3-二甲氧基-邻羟苯亚甲基-4,5-二甲氧基-1,2-苯二胺)、H₂L²(N,N'-3-二甲氧基-邻羟苯亚甲基-4,5-二硝基-1,2-苯二胺)及相应的镍、铜、锌金属配合物ML¹、ML² (M=Ni, Cu,Zn), 并分别采用核磁共振(¹H NMR)波谱、紫外-可见(UV-Vis)吸收光谱、红外(IR)光谱、质谱(MS)和元素分析进行了表征. 探究了配体及其配合物的荧光性质. 研究发现, 与H₂L¹相比, 配体H₂L²由于引入强的吸电子基团―NO₂, 其荧光强度减弱. 相对于配体, 锌离子的配位则导致其配合物的荧光强度增强, 而镍和铜离子的嵌入则使得配合物ML¹、ML² (M=Ni, Cu)荧光猝灭. 对电化学性质的研究表明, CuL1的氧化还原过程为准可逆的单电子过程; 与H₂L²相比, 配体H₂L¹由于引入强的给电子基团―OCH₃, 其溶液的导电性降低.

关键词: Salen型化合物, 合成与表征, 谱学性质, 电化学性质, 荧光性质

Abstract: Two new Salen ligands H₂L¹ (N,N'-bis(3-dimethoxy-salicylidene)-4,5-dimethoxy-1,2- phenylenediamine) and H₂L² (N,N'-bis(3-dimethoxy-salicylidene)-4,5-dinitryl-1,2-phenylenediamine), and their nickel, copper, and zinc complexes ML¹, and ML² (M=Ni, Cu, Zn) were synthesized. The compounds synthesized were characterized by 1H-nuclear magnetic resonance (¹H NMR), ultraviolet-visible absorption spectrometry (UV-Vis), infrared (IR) spectrometry, mass spectroscopy (MS), and elemental analysis. The fluorescence properties of the complexes were also studied. The fluorescence intensity of ligand H₂L² was lower than that of ligand H₂L¹, because of the introduction of the strong electron-withdrawing group, ―NO₂. Moreover, the fluorescence intensities of the zinc complexes are greater than those of the ligands; however the fluorescence is quenched upon complexing of nickel or copper ions. In addition, the cyclic voltammetry shows that the redox process in CuL1 was a one-electron quasi-reversible charge-transfer. Because of the introduction of the electron-donating group ―OCH₃, the solution conductivity of ligand H₂L¹ was lower than that of H₂L².

Key words: Salen-type complex, Synthesis and characterization, Spectrum property, Electrochemical property, Fluorescence property

刘佳, 郭莉芹, 张晓红, 阮文娟, 朱志昂. Salen型化合物的合成、表征及性质[J]. 物理化学学报, 2012, 28(02), 265-272. doi: 10.3866/PKU.WHXB201111251

LIU Jia, GUO Li-Qin, ZHANG Xiao-Hong, RUAN Wen-Juan, ZHU Zhi-Ang. Synthesis, Characterization and Properties of Salen-Type Complexes[J]. Acta Phys. -Chim. Sin. 2012, 28(02), 265-272. doi: 10.3866/PKU.WHXB201111251

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201111251

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I02/265

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Salen型化合物的合成、表征及性质

Synthesis, Characterization and Properties of Salen-Type Complexes

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