Synthesis and Functional Organization of Multiply N-Confused Porphyrins

多重N-混淆卟啉的合成和功能组织

• 批准号: 13440189
• 负责人: FURUTA Hiroyuki
• 金额: $ 6.85万
• 依托单位: Kyushu University (2002)Kyoto University (2001)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13440189/
• 关键词: Porphyrin; N-Confused porphyrin; Porphyrin Isomer; Metal Complex; Calixphyrin; Expanded Porphyrin; Hexphyrin; Aromaticity

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.

用密度泛函理论（DFT）方法计算了95种氮杂卟啉（NCP）异构体的总电子能和非核依赖化学位移（NICS）。芳香性和稳定性没有直接关系。混乱的引入降低了稳定性。18 kcal/mol/次混淆。顺式双氮杂卟啉（N2 CP）的合成结果部分支持了上述结论。此外，不同类型的卟啉类化合物，如corrorin，oxyindolophyrin和tripyrinone，在N2 CP和NCP金属络合反应中得到。研究了N_2CP金属配合物的电化学和光化学性质，并指出其在水裂解和光动力学治疗中的应用潜力。另一方面，合成了一系列卟啉衍生物，包括五卟啉、六卟啉、八卟啉和九卟啉，并通过X-射线单晶分析确定了其结构。一般的meso-芳基取代的膨胀卟啉是非平面的，而双N-混乱的六卟啉是平面的，可以在空腔中与双金属离子络合，保持芳香性，其内、外金属配位更为普遍。以Pd（II）和Pt（II）为催化剂，分别合成了独特的双层结构的面对面二聚体和线性连接的二聚体。当使用Zn（II）和Cd（II）时，形成新型的金属桥连二聚体。明确阐明了NCP金属配位的一种通用模式，为金属辅助超分子组装开辟了道路。

项目成果

Alagar, S.: "Doubly N-Confused Hexaphyrin : A Novel Aromatic Expanded Porphyrin that Complexes Bis-Metals in the Core"J.Am.Chem.Soc.. 125. 878-879 (2003)

Alagar, S.：“双 N 混淆六菲林：一种新型芳香族扩展卟啉，可在核心中络合双金属”J.Am.Chem.Soc.. 125. 878-879 (2003)

Furuta, H.: "Oxyindolophyrin : A Novel Fluoride Receptor Derived from N-Confused Corrole Isomer"J. Am. Chem. Soc.. 123. 6435-6436 (2001)

Furuta, H.：“氧吲哚啉：一种源自 N-混淆的咔咯异构体的新型氟化物受体”J。

Maeda, H.: "N-Confused Porphyrin Bearing meso-Perfluorophenyl Groups : A Potential Agent that Forms Stable Squareplanar Complexes with Cu(II) and Ag(III)"Org. Lett.. 5. 1293-1296 (2003)

Maeda, H.：“带有内消旋全氟苯基的 N-混淆卟啉：一种与 Cu(II) 和 Ag(III) 形成稳定方形平面络合物的潜在试剂”Org。

Maeda, H.: "N-Confused Porphyrin Bearing meso-Perfluorophenyl Groups : A Potential Agent that Forms Stable Squareplanar Complexes with Cu(II) and Ag(III)"Org. Lett.. 5(印刷中). (2003)

Maeda, H.：“N-混乱的带有内消旋全氟苯基的卟啉：与 Cu(II) 和 Ag(III) 形成稳定的方形平面复合物的潜在试剂”Org.. 5（出版中）。

K.Araki: "Acid-Base and Spectro electro chemcil Properties of Dovlly N-Confused Porphyin"Inorg. Chem.. 40. 2020-2025 (2001)

K.Araki：“Dovlly N-混淆卟啉的酸碱和光谱电化学性质”Inorg。