| 一种新型的平面共轭的酞菁卟啉二联体的合成及光谱研究(英文) |
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| 引用本文： | 王 康,齐冬冬,Mack John,王海龙,李文军,边永忠,小林长夫,姜建壮.一种新型的平面共轭的酞菁卟啉二联体的合成及光谱研究(英文)[J].无机化学学报,2012,28(9):1779-1789. |
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| 作者姓名： | 王 康 齐冬冬 Mack John 王海龙 李文军 边永忠 小林长夫 姜建壮 |
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| 作者单位： | 1. 北京科技大学化学与生物工程学院,功能分子与晶态材料科学与应用北京市重点实验室,北京 100083
2. 日本东北大学理学院化学系,仙台 980-8578,日本 |
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| 基金项目： | 国家自然科学基金(No.2012CB224801);日本教育部科学创新基金(No.20108007)资助项目 |
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| 摘 要： | 5,10,15,20-四(4-氯苯基)-2′,3′-二氰基2,3-β]卟啉和4,5-二(丁烷氧基)邻二氰基苯在锂存在的条件下在正戊醇中回流四聚,然后用醋酸处理得到了一种新型的平面共轭酞菁二联体H4{(DAPc(OC4H9)6]TClPP]}(1)(其中DAPc(OC4H9)6是2,3,9,10,16,17-六(丁烷氧基)-22,25-二氮杂酞菁的二价阴离子,TClPP是5,10,15,20-四(4-氯苯基)卟啉的二价阴离子)。这种二联体和Zn(OAc)2.2H2O在DMF和甲苯混合溶剂中反应得到双金属配合物Zn2{(DAPc(OC4H9)6](TClPP)]}(2)。质谱和核磁共振光谱等一系列的表征方法证明了这种双核的混杂四吡咯结构。电子吸收光谱和磁圆二色谱证明了酞菁发色团和卟啉发色团之间存在有效的分子内电子相互作用。这一结论进一步得到了理论计算的支持。
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| 关 键 词： | 四吡咯化合物 酞菁 卟啉 共轭二联体 混杂双核 |
Fusing Phthalocyanine and Porphyrin together: Unprecedented Co-planar Ring-Fused Diazaphthalocyaninato-porphyrin Dimers |
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| WANG Kang,QI Dong-Dong,Mack John,WANG Hai-Long,LI Wen-Jun,BIAN Yong-Zhong,KOBAYASHI Nagao and JIANG Jian-Zhuang.Fusing Phthalocyanine and Porphyrin together: Unprecedented Co-planar Ring-Fused Diazaphthalocyaninato-porphyrin Dimers[J].Chinese Journal of Inorganic Chemistry,2012,28(9):1779-1789. |
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| Authors: | WANG Kang QI Dong-Dong Mack John WANG Hai-Long LI Wen-Jun BIAN Yong-Zhong KOBAYASHI Nagao and JIANG Jian-Zhuang |
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| Institution: | Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China,Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China,Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan,Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China,Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China,Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China,Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan and Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry, University of Science and Technology Beijing, Beijing 100083, China |
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| Abstract: | An unprecedented ring-fused co-planar diazaphthalocyaninato-porphyrin dimer H4{(DAPc(OC4H9)6] TClPP]}(where DAPc(OC4H9)6 is the dianion of 2,3,9,10,16,17-hexa(butyloxy)-22,25-diazaphthalocyanine,and TClPP is the dianion of 5,10,15,20-tetra(4-chloro)porphyrin)(1) was synthesized by mixed cyclic tetramerization of 5,10,15,20-tetrakis(4-chlorophenyl)-2′,3′-dicyanopyrazino2,3-β] porphyrin with 4,5-di(butyloxy)phthalonitrile in the presence of lithium in refluxing n-pentanol followed by treatment with acetic acid.Reaction of the metal free dimer with Zn(OAc)2.2H2O in DMF and toluene led to the isolation of a bimetallic zinc(Ⅱ) complex Zn2{(DAPc(OC4H9)6] (TClPP)]}(2).The binuclear and mixed tetrapyrrole ring nature of the structure was clearly demonstrated by a series of characterization methods including mass spectrometry and NMR spectroscopy.The Q band region of the electronic absorption and magnetic dichroism(MCD) spectra provide evidence for significant intramolecular interaction between the phthalocyanine and porphyrin chromophores.Theoretical calculations provide further support for this. |
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| Keywords: | tetrapyrrole phthalocyanine porphyrin conjugated dimer mixed binuclear |
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