Synthesis and Functional Organization of Multiply N-Confused Porphyrins

用密度泛函理论(DFT)方法计算了95个N-混杂卟啉(NCP)异构体的总电子能量和非核化学位移(NICS)。香气性质与稳定性无直接关系。混淆的引入降低了稳定性，每一次混淆约为18千卡/摩尔。实验结果部分支持了顺式双N-混淆卟啉(N2CP)的实际合成。此外，在N2CP和NCP的金属络合反应中，还得到了不同类型的卟啉类化合物，如科罗林、氧化吲哚叶琳和三吡咯酮。研究了N_2CP金属络合物的电化学性质和光化学性质，展望了其在水分解和光动力学治疗(PDT)中的应用前景。另一方面，合成了一系列扩展的卟啉化合物，包括戊四氢叶酸、己烷酸、八氢吡喃和非丙氨酸，并通过X-射线单晶分析确定了它们的结构。正规型的中位芳基取代的扩展卟啉是非平面的，而双N杂化的六氢卟啉是近平面的，可以与腔内的双金属离子配位，保持芳香性。以Pd(II)和Pt(II)为原料，分别合成了独特的双层面对面二聚体和线状连接二聚体。当使用锌(II)和镉(II)时，形成了一种新型的金属桥联二聚体。明确阐明了NCP金属配位的多种方式，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.