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

(1)多桥[3_n]环番（n=3-6）光异构化法合成六棱柱衍生物。我们对六棱柱衍生物的分离和表征进行了努力。为了稳定六棱柱骨架并使其对化学反应失活，我们开发了新的合成方法，以氟化[3_n]环烷作为光化学反应的前驱体。我们证实了这些环番的光化学反应确实进行了。光产物的分离和表征正在进行中。作为分离六柱甾衍生物的一种替代方法，我们发现[3_3]环烷以1:1的比例包含在γ-环糊精中，并分离了配合物。在固体状态下照射配合物会形成一些笼状化合物，它们的分离和表征正在进行中。2)合成管状分子作为新的包裹体宿主分子为了构建单分子管状分子，我们合成了具有不同空腔大小的新型环烷作为结构单元，并对其结构性质进行了研究。我们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个三维的新大环。(3)含环烷配体的茂金属的合成及其性质我们研究了铁原子被高度压缩的[3_5]二茂铁的合成路线。作为一种新的合成路线，我们设计了烯烃复分解环化法合成二茂铁。根据这条路线，合成正在进行中。我们还研究了Ru(II)Ru(0)-[3_n]环烷（n=3,4）混合价配合物作为新型导电材料的合成。我们发现Ru(I)Ru(I)配合物是由Ru(II)Ru(II)-[3_3]环烷配合物的双电子还原形成的，并对其结构和化学性质进行了研究。

(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.