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.

采用密度泛函理论（DFT）方法计算了N-混淆卟啉（NCP）95种异构体的总电子能和核无关化学位移（NICS）。芳香性质和稳定性没有直接关系。混乱的引入会降低稳定性。每1次混乱18 kcal/mol。顺式双N-混淆卟啉（N2CP）的实际合成部分支持了该结果。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。对N2CP金属配合物的电化学和光化学进行了研究，并提出了其在水分解和光动力疗法（PDT）中的应用潜力。另一方面，合成了一系列扩展卟啉，包括五菲林、六菲林、八菲林和九菲林，并通过X射线单晶分析确定了结构。正常类型的内消旋芳基取代的扩展卟啉是非平面的，但双N-混淆的六菲林是平面的，可以在空腔中络合双金属离子，保持芳香性。NCP的内部和外部金属配位被发现更普遍。利用Pd(II)和Pt(II)，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，形成了一种新型金属桥联二聚体。明确阐明了 NCP 金属配位的通用模式，并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。