Synthesis and Functional Organization of Multiply N-Confused Porphyrins

用密度泛函理论（DFT）计算了95种n -杂化卟啉（NCP）异构体的总电子能和核无关化学位移（NICS）。芳香性与稳定性无直接关系。混和物的引入使溶液的稳定性降低，每混和物降低约18千卡/摩尔。实际合成的顺式双n络合卟啉（N2CP）部分支持了这一结果。此外，在N2CP和NCP金属络合反应中，得到了不同类型的卟啉类化合物，如corrorin、oxyindolophyrin和tripyrrinone。研究了N2CP金属配合物的电化学和光化学性质，并提出了其在水裂解和光动力治疗（PDT）方面的应用前景。另一方面，合成了一系列扩展的卟啉，包括五葡萄蛋白、六葡萄蛋白、八葡萄蛋白和非葡萄蛋白，并通过x射线单晶分析确定了它们的结构。正常型的介芳基取代的扩展卟啉是非平面的，而双n混淆的六葡萄蛋白是平面的，可以在腔内络合金属离子，保持芳香性。新型冠状病毒的内外金属配位更为普遍。以Pd（II）和Pt（II）为原料，分别合成了独特的双层型面对面二聚体和线性连接二聚体。当使用Zn（II）和Cd（II）时，形成了一种新型的金属桥接二聚体。明确阐明了NCP金属配位的多用途模式，为金属辅助超分子组装开辟了道路。

The total electronic energy and nucleus-independent chemical shift (NICS) of 95 isomers of N-confused porphyrin (NCP) have been calculated by density functional theory (DFT) method. The aromatic nature and the stability were not directly related. The introduction of confusion decreases the stability ca. 18 kcal/mol per one confusion. The results were partially supported by the actual synthesis of cis-doubly N-confused porphyrin (N2CP). Furthermore, a different type of porphyrinoids, such as corrorin, oxyindolophyrin, and tripyrrinone, were obtained in the reactions of N2CP and NCP metal complexation. Electrochemistry and photochemistry of N2CP metal complexes were investigated and the potentiality for the use in water splitting and photodynamic therapy (PDT) were suggested.On the other hand, a series of expanded porphyrins including, pentaphyrin, hexaphyrin, octaphyrins, and nonaphyrins, were synthesized and the structures were determined by the X-ray single crystal analyses. The normal type of meso-aryl substituted expanded porphyrins were non-planar but the doubly N-confused hexaphyrins were fond planar and could complex bis metal ions in the cavity maintaining the aromaticity.The inner and outer metal coordination were found more general for the NCP. By using Pd(II) and Pt(II), unique double-decker type face-to-face dimers and the linear linked dimers were synthesized, respectively. When Zn(II) and Cd(II) were used, a new type of metal bridged dimers were formed. A versatile mode of NCP metal coordination were explicitly elucidated and opened the way for the metal assisted supramolecular assembly.