A Study on the Synthesis, Structure, Reaction, and Properties of New π-Elecitronic Macrocycles

新型π电子大环化合物的合成、结构、反应及性能研究

• 批准号: 14340200
• 负责人: SHINMYOZU Teruo
• 金额: $ 9.41万
• 依托单位: Kyushu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340200/
• 关键词: prismanes; cage compounds; metallocene; cyclophane; charge transfer complexes; charge transfer interaction; conducting materials; photochemical reaction; プリズマン類; 芳香族化合物; ヘキサプリズマン; チューブ状分子; フェロセン

(1)Synthesis of hexaprismane derivatives via photo-isomerization of multibridged[3_n]cyclophanes(n=3-6)Our efforts have been made toward the isolation and characterization of hexaprismane derivatives. In order to stabilize the hexaprismane skeleton and deactivate toward chemical reactions, we developed new synthetic methods of fluorinated[3_n]cyclophanes as precursor of the photochemical reactions. We confirmed that the photochemical reactions of these cyclophanes did proceed. The isolation and characterization of the photoproducts are in progress.As an alternative method for the isolation of hexaprismane derivatives, we found that the[3_3]cyclophane is included in γ-cyelodextrine in 1:1 ratio and the complex is isolated. Irradiation of the complex in the solid state led to the formation of some cage compound(s), and their isolation and characterization are in progress.2)Synthesis of tube-like molecules as new inclusion host moleculesFor the construction of uni-molecular tube-like molecule, we synthesized the new cyclophanes with different cavity sizes as structural units and examined their structural properties. We are now studying connecting methods of these structural units. In connection with this study, we also designed and synthesized several three-dimensional new macrocycles via metal coordination.(3)Synthesis and properties of metallocenes with cyclophane ligandsWe have studied the synthetic route of [3_5]ferrocenophane in which an iron atom is highly compressed. As a new synthetic route, we designed to synthesize the ferrocenophane by the cyclization using olefin-metathesis. According to this route, synthesis is in progress.We also studied the synthesis of mixed valent Ru(II)Ru(0)-[3_n]cyclophane(n=3,4) complexes as new electron-conducting materials. We found that the Ru(I)Ru(I) complex was formed by the two-electron reduction of the Ru(II)Ru(II)-[3_3]cyclophane complex, and examined its structure and chemical properties.

（1）通过多桥[3-n]环番（n=3-6）的光异构化反应合成六癸烷衍生物为了稳定六癸烷的骨架并使其对化学反应失活，我们开发了新的合成方法，以[3_n]环番为光化学反应的前体。我们证实了这些环番的光化学反应确实进行。作为一种分离六癸烷衍生物的替代方法，我们发现[3_3]环番以1：1的比例包合在γ-环糊精中，并分离出复合物。2）管状分子作为包合主体分子的合成为了构建单分子的管状分子，我们合成了具有不同空腔大小的新型环番作为结构单元，并研究了它们的结构性质。我们现在正在研究这些结构单元的连接方法。结合本研究，我们还通过金属配位设计合成了几种新型的三维大环化合物。（3）含环蕃配体的二茂铁的合成与性质研究了含铁原子高度压缩的[3_5]二茂铁并蕃的合成路线。作为一条新的合成路线，我们设计了烯烃复分解环合法合成二茂铁甲环。本文还研究了新型电子导电材料Ru（II）Ru（0）-[3_n]环蕃（n= 3，4）混合价配合物的合成。我们发现Ru（I）Ru（I）配合物是由Ru（II）Ru（II）-[3_3]环蕃配合物经双电子还原而形成的，并研究了它的结构和化学性质。

项目成果

M.Zhou et al.: "An Aldol Approach to the Synthesis of [3_4](1,2,3,4)Ferrocenophane and its Structural and Electrochemical Properties"J. Organoment.Chem.. (in press). (2004)

M.Zhou等：“[3_4](1,2,3,4)二茂铁的醇醛合成方法及其结构和电化学性能”J.

Mikio Yasutake et al.: "Structural and Electric Properties of the Charge Transfer Complexes of 5,7,9-Trimenthyl-and 2,11,20-trithia[3_3](1,3,5)cyclophanes"Eur. J. Org. Chem.. (in press). (2003)

Mikio Yasutake 等人：“5,7,9-三薄荷基-和 2,11,20-三硫杂[3_3](1,3,5)环烷的电荷转移络合物的结构和电学性质”Eur.

Mikio Yasutake et al.: "Structural and Electric Properties of the Charge Transfer Complexes of 5,7,9-Trimethyl-and 2,11,20-trithia[3_3](1,3,5)cyclophanes."Eur.J.Org.Chem.. 1343-1347 (2003)

Mikio Yasutake 等人：“5,7,9-三甲基-和 2,11,20-三硫[3_3](1,3,5)环芳烃的电荷转移络合物的结构和电学性质。”Eur.J.

Teruo Shinmyozu et al.: "CRC Handbook of Organic Photochemistry and Photobiology, 2^<nd> Edition(W.Horspool, F.Lenci(Eds))"CRC Press. 1000 (2003)

Teruo Shinmyozu 等：“CRC Handbook of Organic Photochemistry and Photobiology, 2^<nd> Edition(W.Horspool, F.Lenci(Eds))”CRC Press。

Gang Wen et al.: "A Conformational Study of 2,11-Diaza[3.3]metacyclophanes"J.Am.Chem.Soc.. (in press). (2004)

Gang Wen 等人：“2,11-Diaza[3.3]metacyclophanes 的构象研究”J.Am.Chem.Soc.（出版中）。