Synthesis of tetrapyrrolic N-confused porphyrinoids and exploration their function

为了探索从n -杂化卟啉的发现开始的“n -杂化卟啉”的化学性质，主要研究了NCP的金属配位和n -杂化扩展卟啉的合成。当典型的三脚配合物Re与NCP配体进行金属配位时，得到了不寻常的n -熔融卟啉Re配合物，其混乱的吡咯环被反转并与卟啉核心中相邻的吡咯环融合。我们进一步将该配合物氧化得到稀土三氧配合物，有效地催化了氧转移反应。在杂化扩张卟啉的合成过程中，得到了几种新的杂化八卟啉及其配合物。从八叶林配合物的x射线分析中，提出了引入混乱的吡咯环释放应变能的可能性。此外，还发现了双混淆的六葡萄素配合物具有近红外发射和多重氧化还原等新特性。另一方面，新合成了一种不同类型的杂化卟啉，如吡唑卟啉。认为该合成方法适用于其他多混相卟啉。

To explore the chemistry of "N-confused porphyrinoids" that has been started from the finding of N-confused porphyrin, metal coordination of NCP and synthesis of N-confused expanded porphyrins were mainly studied.When Re, a typical metal that can afford a tripodal complex, was subjected for the metal coordination to an NCP ligand, unusual N-fused porphyrin Re complex, whose confused pyrrole ring is inverted and fused to an adjacent pyrrole ring in the porphyrin core, was obtained. This complex we further oxidized to afford a Re trioxo-complex, which catalyzed an oxygen transfer reaction efficiently.In the synthesis of the confused expanded porphyrins, several new confused octaphyrins and their complexes were obtained. From the x-ray analysis of the octaphyrin complexes, the release of the strain energy by the introduction of confused pyrrole rings was suggested. Furthermore, several new features including near infrared emission and multi-redox were revealed with the doubly confused hexaphyrin complexes.On the other hand, a different type of confused porphyrin such as pyrazole porphyrin was newly synthesized. The synthetic methodology is thought applicable to other multi-confused porphyrins.