Development of Chemistry of Expanded Porphyrins

大的环尺寸的扩张的卟啉鼓励了相关的多金属络合物的形成的可能性。沿着这条线，我们研究了八毛精的铜(II)金属化，这导致了双铜(II)八毛精的定量形成。有趣的是，这种双铜(II)八氢吡喃的加热导致分裂成两个铜(II)卟啉。我们将这个有趣的反应命名为分子有丝分裂。这一反应伴随着很大的光谱变化，可用于存储器件。因此，我们制备了一种由双铜(II)八氢吡喃组成的薄膜，它被发现比在溶液中更能抵抗热分裂。我们还研究了去氢化物的铜(II)金属化，这导致了两个被发现具有非常独特结构的三铜(II)去氢化物的分离，其中边缘的两个铜(II)离子配位在半卟啉状的四吡咯配体中，而中心的铜(II)离子只与吡咯氮原子配位。我们还考察了以三吡喃为起始底物的扩张型卟啉的尺寸选择性合成。从这个反应中，我们分离出了红宝石红、非金黄色葡萄素、十二烷基胡萝卜素，其中一些被发现作为阴离子敏感剂是有用的。

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.