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Development of Chemistry of Expanded Porphyrins

扩展卟啉的化学进展

基本信息

批准号：
15350022
负责人：
OSUKA Atsuhiro
金额：
$ 9.34万
依托单位：
Kyoto University
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
起止时间：
2003 至 2004
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15350022/
关键词：
porphyrins expanded porphyrins aromaticity metal complexes size-selective synthesis hexaphyrins octaphyrins

项目摘要

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.

膨胀卟啉的大环尺寸鼓励相关的多金属配合物的形成的可能性。沿着这条线，我们研究了铜（II）金属化的八卟啉，这导致形成双铜（II）八卟啉定量。有趣的是，这种bis-Cu（II）octaphyrin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。该反应伴随着大的光谱变化，其可用于存储器件。因此，我们制备了由bis 0 Cu（II）八卟啉组成的膜，发现其比在溶液中更能抵抗热裂解。我们还研究了十卟啉的Cu（II）金属化，这导致分离出两种三-Cu（II）十卟啉，发现其显示出非常独特的结构，其中边缘的两个Cu（II）离子配位在半卟啉状的四吡咯配体中，而中心的Cu（II）离子仅与吡咯氮原子配位，构成了一种非常罕见的情况。从这个反应中，我们分离出了红比林，九卟啉，十二卟啉，其中一些被发现是有用的阴离子传感剂。

项目成果

期刊论文数量（180）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Anion Binding Properties of N-Confused Porphyrins at the Peripheral Nitrogen

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

A dodecameric porphyrin wheel.

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