六种酞菁锌配合物:交叉聚合法合成、分离、光谱和电化学性质
Six Phthalocyaninato Zinc(Ⅱ) Complexes:Synthesis via Cross-Condensation of Two Phthalonitriles, Spectroscopy and Electrochemistry
作者单位E-mail
柏铭 山东大学(威海)海洋学院, 威海 264209 ming_bai@sdu.edu.cn 
张岩 山东大学(威海)海洋学院, 威海 264209  
万培红 山东大学(威海)海洋学院, 威海 264209  
张崇禧 山东大学(威海)海洋学院, 威海 264209  
摘要: 使用2种前驱体121=4,5-二(4-甲酯基)酚氧取代邻苯二甲腈,2=4-二缩三乙二醇单甲醚取代邻苯二甲腈)与Zn(OAc)2·2H2O在DBU(1,8-二氮杂双环[5.4.0]十一碳-7-烯)催化下,在正戊醇中进行酯交换及交叉聚合反应得到6种酞菁锌配合物。通过简单的硅胶柱色谱,可以将这6种配合物Zn[Pc(BP)4](3),Zn[Pc(BP)3(TEG)](4),Zn[Pc(BP)2(TEG)2]-opp(5),Zn[Pc(BP)2(TEG)2]-adj(6),Zn[Pc(BP)(TEG)3](7)和Zn[Pc(TEG)4](8)进行分离。对合成的6种化合物进行了质谱,元素分析,紫外-可见吸收光谱,核磁共振谱表征。另外,对这些化合物的电化学性质也进行了研究。
关键词: 交叉聚合  酯交换  酞菁  核磁共振谱  电化学
基金项目: 国家自然科学基金(No.21001069)资助项目。
Abstract: Cross-condensation of two different phthalonitriles, namely 4,5-bis[(4-methyloxycarbonyl)phenoxy]phthalonitrile (1) and 4-{2-[2-(2-methoxyethoxy)ethoxy]ethoxy}phthalonitrile(2), in the presence of Zn(OAc)2·2H2Oand 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) followed by transesterification in refluxing n-pentanol afforded six phthalocyaninato zinc(Ⅱ) complexes modulated with different numbers of pentyloxycarbonyl and/or triethylene glycol monomethyl ether groups. Simple silica-gel column chromatography leads to the successful separation of all these six compounds, namely Zn[Pc(BP)4](3), Zn[Pc(BP)3(TEG)](4), Zn[Pc(BP)2(TEG)2]-opp(5), Zn[Pc(BP)2(TEG)2]-adj(6), Zn[Pc(BP)(TEG)3](7), and Zn[Pc(TEG)4](8). In addition, the six complexes have been characterized with elemental analysis, MALDI-TOFmass, UV-Vis spectroscopy, 1H NMR, and 2D COSYspectroscopy. The electrochemical properties have also been investigated.
Keywords: cross-condensation  esterification  phthalocyanines  NMR spectroscopy  electrochemical property
投稿时间:2013-06-07 修订日期:2013-09-02
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柏铭,张岩,万培红,张崇禧.六种酞菁锌配合物:交叉聚合法合成、分离、光谱和电化学性质[J].无机化学学报,2014,30(2):371-378.
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