Development of Chemistry of Expanded Porphyrins

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。

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.