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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (08): 949-954. 上一篇    下一篇

研究论文

α和β-四(4-甲氧基苯氧基)酞菁锌的合成、表征和电化学性质

白青龙1,2，张春花2，程传辉*,1，李万程3，杜国同1,3   

  1. (1大连理工大学物理与光电工程学院 三束材料改性国家重点实验室 大连 116023)
    (2内蒙古民族大学化学与化工学院 通辽 028043)
    (3吉林大学电子科学与工程学院 吉林大学集成光电子国家重点实验室 长春 130012)
  • 投稿日期:2010-09-12 修回日期:2010-10-21 发布日期:2010-12-27
  • 通讯作者: 程传辉 E-mail:chengch79@yahoo.cn
  • 基金资助:

    国家自然科学基金项目;高等学校博士学科点专项科研基金;中央高校基本科研业务费专项资金

Studies on Electrochemical Properties of α- and β- Tetrakis(4-methoxyphenoxy)phthalocyaninatozinc

Bai Qinglong1,2 Zhang Chunhua2 Cheng Chuanhui*,1 Li Wancheng3 Du Guotong1,3   

  1. (1 State Key Laboratory of Materials Modification by Laser, Ion and Electron Beams, School of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116023)
    (2 College of Chemistry and Chemical Engineering, Inner Mongglia University for Nationalities, Tongliao 028043)
    (3 State Key Laboratory of Integrated Optoelectronics, Jilin University, Changchun 130012)
  • Received:2010-09-12 Revised:2010-10-21 Published:2010-12-27
  • Supported by:

    ;Fundamental Research Funds for the Central Universities

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以3-硝基邻苯二腈和4-硝基邻苯二腈为原料经过两步反应合成了α和β-四甲氧基苯氧基酞菁锌, 通过IR光谱、UV-Vis光谱、MS谱、1H NMR谱和元素分析表征了其结构, 其结果与标题化合物的结构一致. 这两种酞菁在有机溶剂中有良好的溶解性. 通过循环伏安法研究其能带结构和电化学过程, 结果表明, 甲氧基苯氧基在α-位时(与苯氧基在β-位时相比)酞菁单体的HOMO能级升高, LUMO能级降低, 带隙变窄, 有利于酞菁分子的电子传输. 它们在二氯甲烷中的电化学过程都是单电子准可逆过程, 而且氧化还原过程均发生在酞菁环上. 最后提出了两种酞菁的电化学反应机理.

关键词: 甲氧基苯氧基, 循环伏安法, 能带结构, 电化学过程, 反应机理

With 3-nitrobenzene-1,2-dicarbonitrile and 4-nitrobenzene-1,2-dicarbonitrile as raw materials, α- and β-tetrakismethoxyphenoxy phthalocyaninatozinc were synthesized via two-step reaction. The structure of two compounds were characterized by IR, UV-Vis, MS, 1H NMR spectra and elemental analysis, and the results are consistent with the structures of title compounds. Two phthalocyanine compounds have good solubility in organic solvents. The energy band structures and electrochemical processes were studied by cyclic voltammetry. The results indicated the phthalocyanine monomer has higher HOMO energy levels, lower LUMO energy levels and more narrow band gap when the methoxyphenoxy lies on α-site than on β-site, which are favorable for the electron transfer of phthalocyanine molecules. The results showed that the electrochemical processes of two compounds were all quasi-reversible single-electron processes in dichloromethane, and the oxidation-reduction reactions occurred in phthalocyanine ring. Finally, the electrochemical reaction mechanism of two phthalocyanine compounds were put forward.

Key words: methoxyphenoxy, cyclic voltammetry, energy band structure, electrochemical processes, reaction mechanism