COORDINATION CHEMISTRY AND ELECTROCHEMISTRY OF LAYERED MOLECULAR SYSTEMS MADE OF PORPHYRINS WITH DIFFERENT REDOX PROPERTIES.

具有不同氧化还原性质的卟啉层状分子系统的配位化学和电化学。

• 批准号: 09640666
• 负责人: SETSUNE Jun-ichiro
• 金额: $ 1.92万
• 依托单位: KOBE UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640666/
• 关键词: porphyrin; bisporphyrin; polynuclear complex; redox

Dimeric porphyrins have been drawing much attention as structural units for multi-electron redox systems. Two porphyrins are linked by covalent bonding between substituents at the porphyrin periphery or by ligand bonding between central metals, as approaches by organic chemistry and coordination chemistry, respectively. Since structural factors such as inter-ring distance and orientation between two porphyrin plane make great influence on the multi-electron redox functions, this work was intended to create new bisporphyrin framework. The research achievements are as following.(1) We had already found that unusual (CH=CH-N,N')-link can be made between pyrrole nitrogen s of two porphyrins by one-step reaction between Co(III) porphyrin and acetylene. We have established experimental conditions and yields for combinations of various porphyrins in this coupling reaction. (2) We have prepared various mixed binuclear complexes of bisporphyrin with combinations of Zn, Cu, and Co in good yields and determined their spectroscopic properties and X-ray crystal structure. (3) We have shown that unusual tris- and tetrakis-porphyrins metallated with Zn, Cu, Co, and Fe are easily synthesized. In particular, a Fe-O-Fe link was readily constructed to lead to mixed-metal tetrakisporphyrins.The bisporphyrins with unusual spacers between pyrrole nitrogens have been shown to be useful as the building block for layered porphyrin systems.

二聚体卟啉作为多电子氧化还原体系的结构单元受到了广泛的关注。两个卟啉通过卟啉外围取代基之间的共价键或中心金属之间的配体键连接，分别通过有机化学和配位化学方法连接。由于两个卟啉平面之间的环间距和取向等结构因素对多电子氧化还原功能有很大影响，本工作旨在构建新的双卟啉框架。研究成果如下：(1)我们已经发现，在Co（III）卟啉与乙炔的一步反应中，两种卟啉的吡咯氮s之间可以形成异常的（CH=CH-N，N'）链。我们建立了各种卟啉在该偶联反应中组合的实验条件和产率。(2)我们以较好的产率制备了多种双卟啉混合双核配合物，并测定了它们的光谱性质和x射线晶体结构。(3)我们已经证明了用Zn、Cu、Co和Fe金属化的不寻常的三和四卟啉是很容易合成的。特别是，Fe-O-Fe连接很容易形成混合金属四异卟啉。在吡咯氮之间具有不寻常间隔的双卟啉已被证明是有用的层状卟啉系统的构建块。

项目成果

J.Setsune: "Synthesis of Vinylene-Co, N'-Linked Multi (porphyrin)s by the Addition of Free Base Porphyrins to a C_2H_2 Complex of Co^<III> Porphyrin and Their Oxidative Rearrangement to Vinylene-N,N'-Linked Multi (porphyrin)s" Inorg.Chem.37. 2235-2246 (19

J.Setsune：“通过将游离碱卟啉添加到 Co^<III> 卟啉的 C_2H_2 复合物中合成亚乙烯基-Co, N-连接的多（卟啉）及其氧化重排为亚乙烯基-N,N-

J.Setsune: "Synthesis of Vinylene-Co,N′-Linked Multi (porphyrin) s by the Addition of Free Base Porphyrins to a C_2H_2 Complex of Co^<III> Porphyrin and Their Oxidative..." Inorg.Chem.37(印刷中). (1998)

J.Setsune：“通过将游离碱卟啉添加到 Co^<III> 卟啉的 C_2H_2 复合物中合成亚乙烯基-Co,N-连接的多（卟啉）及其氧化......” Inorg.Chem.37 （出版中）。

J.Setsune: "Synthesis of Vinylene-Co, N'-Linked Multi(porphyrin)s by the addition of Free Base Porphyrins to a C_2H_2 complex of Co^<111> Porphyrin and Their Oxidative Rearrangement to Vinylene..." Inorg.Chem.37. 2235-2246 (1998)

J.Setsune：“通过将游离碱卟啉添加到 Co^<111> 卟啉的 C_2H_2 复合物中合成亚乙烯基-Co、N-连接的多（卟啉）及其氧化重排为亚乙烯基......” Inorg。

J.Setsune: "Reversible Complexation of Acetylene with (Perchlorato) Cobalt (III) Porphyrins to Form a Novel Biscobalt (II) Bisporphyrin with a Vinylene-N,N' Linkage" Organometallics. 16. 597-605 (1997)

J.Setsune：“乙炔与（高氯酸）钴 (III) 卟啉可逆络合，形成具有亚乙烯-N,N 连接的新型双钴 (II) 双卟啉”有机金属化合物。

Y.Takao: "Synthesis of Binuclear Palladium (II) Complexes of Bidentate N (21), N (22)-Bridged Porphyrins" Chem.Lett.761-762 (1996)

Y.Takao：“双齿 N (21)、N (22)-桥卟啉双核钯 (II) 配合物的合成”Chem.Lett.761-762 (1996)