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Development of Chemistry of Expanded Porphyrins

Development of Chemistry of Expanded Porphyrins
扩展卟啉的化学进展
批准号:
15350022
负责人:
OSUKA Atsuhiro
金额:
$9.34万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (B)
财政年份:
2003
资助国家:
日本
项目状态:
已结题
起止时间:
2003 至 2004

项目摘要

项目成果

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中文摘要
翻译
扩展卟啉的大环尺寸促进了相关多金属配合物形成的可能性。沿着这条线,我们研究了Cu(II)金属化导致双Cu(II)八烷基苷的定量形成。有趣的是,这种双Cu(II)八卟啉的加热导致分裂成两个Cu(II)卟啉。我们把这个有趣的反应命名为分子有丝分裂。这一反应伴随着较大的光谱变化,可用于存储器件。我们由此制备了一种由铋cu (II)八叶林组成的薄膜,该薄膜比溶液中更能抵抗热分裂。我们还研究了decaphyrin的Cu(II)-金属化,这导致分离出两个tris-Cu(II) decaphyrin,发现它们具有非常独特的结构,其中边缘的两个Cu(II)离子在半卟啉类四吡啶配体中配位,而中心的Cu(II)离子仅与吡啶氮原子配位,构成非常罕见的情况。我们还研究了以三吡喃为起始底物的扩展卟啉的尺寸选择性合成。从这个反应中,我们分离出了红素、非葡萄蛋白、十二葡萄蛋白,其中一些被发现是有用的阴离子感应剂。
英文摘要
The large ring size of expanded porphyrins encourages the possibility of the formation of related multi-metal complexes. Along this line, we examined the Cu(II) metalation of an octaphyrin, which led to the formation of bis-Cu(II) octaphyrin quantitatively. Interestingly, the heating of this bis-Cu(II) octaphyrin resulted in the splitting into two Cu(II) porphyrins. We named this interesting reaction as a molecular mitosis. This reaction is accompanied by a large spectral change, which may be used in memory devices We thus made a film composed of bis0Cu(II) octaphyrin that was found to be more robust against the thermal splitting than in solution.We also examined the Cu(II)-metalation of a decaphyrin, which led to the isolation of two tris-Cu(II) decaphyrins that were found to show very unique structures, in which the edged two Cu(II) ions are coordinated within a hemi-porphyrin-like tetrapyrrolic ligand, while the central Cu(II) ion is coordinated with only pyrrolic nitrogen atoms, constituting a very rare case.We also examined the size-selective synthesis of expanded porphyrins with a tripyrrane as a starting substrate. From this reaction, we isolated rubyrin, nonaphyrin, dodecaphyrin, some of which were found to be useful as an anion sensing agent.
期刊论文(180)
专著(0)
科研奖励(0)
会议论文
DOI: 10.1023/b:jiph.0000031110.42096.d3
发表时间: 2004-06
期刊: Journal of inclusion phenomena and macrocyclic chemistry
影响因子: 2.3
作者: [H. Maeda;A. Osuka;H. Furuta]
通讯作者: H. Maeda;A. Osuka;H. Furuta
DOI: 10.1021/ja0392972
发表时间: 2004-03
期刊: Journal of the American Chemical Society
影响因子: 15
作者: [Xiaobin Peng;N. Aratani;Akihiko Takagi;T. Matsumoto;T. Kawai;I. Hwang;T. Ahn;Dongho Kim;A. Osuka]
通讯作者: Xiaobin Peng;N. Aratani;Akihiko Takagi;T. Matsumoto;T. Kawai;I. Hwang;T. Ahn;Dongho Kim;A. Osuka
N-Fused Pentaphyrins and Their Rhodium Complexes : Oxidation-induced Rhodium Rearrangement
N-稠合五菲林及其铑配合物:氧化诱导的铑重排
DOI: --
发表时间: 2005
期刊: Chem.Eur.J. 11
影响因子: --
作者: [S.Mori, J.-Y.Shin, S.Shimizu, F.Ishikawa, H.Furuta, A.Osuka]
通讯作者: A.Osuka
M.Suzuki, S.shimizu, J.-Y.Shin, A.Osuka: "Regioselective Nucleophilic Substitution Reaction of meso-Hexakis (pentafluorophenyl) Substituted [26]Hexaphyrin"Tetrahedron Lett.. 44. 4597-4601 (2003)
M.Suzuki、S.shimizu、J.-Y.Shin、A.Osuka:“内消旋六基(五氟苯基)取代的 [26]六面体的区域选择性亲核取代反应”Tetrahedron Lett.. 44. 4597-4601 (2003)
DOI: --
发表时间:
期刊:
影响因子: --
作者: []
通讯作者:
55
    Exploration of Catenated Expanded Porphyrins
    • 批准号:
      25620031
    • 项目类别:
      Grant-in-Aid for Challenging Exploratory Research
    • 资助金额:
      $2.5万
    • 财政年份:
      2013
    • 负责人:
      OSUKA Atsuhiro
    • 依托单位:
    Synthesis and functionalization of discrete porphyrin tube
    • 批准号:
      23655034
    • 项目类别:
      Grant-in-Aid for Challenging Exploratory Research
    • 资助金额:
      $2.5万
    • 财政年份:
      2011
    • 负责人:
      OSUKA Atsuhiro
    • 依托单位:
    Development and functionalization of Mobius aromaticity
    • 批准号:
      22245006
    • 项目类别:
      Grant-in-Aid for Scientific Research (A)
    • 资助金额:
      $29.29万
    • 财政年份:
      2010
    • 负责人:
      OSUKA Atsuhiro
    • 依托单位:
    Development of Novel π-Conjugated Systems Based on Porphyrins
    • 批准号:
      19205006
    • 项目类别:
      Grant-in-Aid for Scientific Research (A)
    • 资助金额:
      $29.12万
    • 财政年份:
      2007
    • 负责人:
      OSUKA Atsuhiro
    • 依托单位:
    海外基金