Formation and Properties of Supramolecular Structures based on Indacene Skeleton

海苯二烯骨架由刚性芳环和柔性五元环组成。通过在沿XYZ轴的位置上引入各种取代基来实现功能化，为骨架提供了构建具有不同性质的分子器件的机会。而且，在2,6取代衍生物中，五元环上的两个体积较小的基团在分子平面上垂直定向。(a)功能化大环的制备及其性质。研究了含(Z)-4,8-二甲氧基羟基- 1多单元的大环的制备及其氧化还原性能，这些大环在2,6位由丁二炔基团连接。三聚体和四聚体表现出与2,6-二乙基羟基苯二烯类似的可逆单波氧化过程，而二聚体则表现出可逆的两段单电子氧化过程，这可以通过羟基苯二烯单元之间的电子相互作用来解释。(b)可逆亚胺键构建的大环的制备及其性质。研究了(Z)-羟基癸二醛2与各种芳香二胺形成亚胺键制备大环的方法。当2和苯二胺3a或1,5-二氨基萘3b的混合物在CDC13或C6D6中放置于室温时，以2:3=2:2的比例主要形成轻溶的大环。还研究了还原四胺大环3的主客体性质。(c)以邻苯二烯为轴分子构建轮烷结构。在(E)-2中，两个体积较小的甲酰基通过形成亚胺键，将两个三苯胺半环连接起来。然后，亚胺衍生物的分子内大环化得到伪轮烷的前体。结果表明，大环的亚胺键在酸性条件下被水解，轴(E)-2在大循环中被脱螺纹。

The hydrindacene skeleton is constituted of a rigid aromatic ring and flexible five-membered rings. Functionalization by introducing various substituents at the positions along the XYZ axes offers the skeleton the opportunities to construct molecular devices with diverse properties. And, in 2,6-substituted derivatives, two less bulky groups on five-membered rings-are vertically oriented oa molecular plane.(a)Preparation and properties of functionalized macrocycles.The preparation and redox properties of the macrocycles containing multiple units of the (Z)-4,8-dimethoxyhydrindacene 1,that are connected at the 2,6-positions by butadiyne groups were studied. The trimer and tetramer exhibit reversible one-wave oxidation process similar to the monomer unit, 2,6-diethynylhydrindacene, while the dimer undergoes a reversible two-stage one-electron oxidation, which can be accounted for by the electronic interaction between the hydrindacene units.(b)Preparation and properties of macrocycles constructed by reversible imine bonds.The preparation of macrocycles by the imine-bond formation between (Z)-hydrindacenedialdehyde 2 and various aromatic diamines were studied. When a mixture of 2 and phenylenediamine 3a or 1,5-diaminonaphthalene 3b in CDC13 or C6D6 left at room temperature, aslightlysoluble macrocycles in a ratio of 2:3=2:2was formed predominantly. Thehost-guest properties of the reduced tetraamine macrocycles 3 were also studied.(c)Construction of rotaxane structure using hydrindacene as the axle molecule.In (E)-2, two less bulky formyl groups work as connecting parts with two terphenylamine half-rings by forming imine bonds. Then, the intramolecular macrocyclization of the imine derivative gave the precursor of the pseudo-rotaxane. It was revealed that imine bonds of the macrocycle were hydrolyzed under acidic condition, and the axle (E)-2 was dethreaded from macrecycle.