Construction and Characterization of Nano-structure based on acethylene macrocycles consisting of the fluorene units.

超分子化学通过非共价键将小分子化合而产生新的功能，一直受到人们的关注。由乙炔单元组成的大环化合物具有内腔。组装这些大环化合物，可以形成超分子结构如管状结构，其可以应用于主体-客体化学等。在本研究中，我们提出了制备基于芴单元取代苯单元的乙炔型大环化合物，并检查其聚集行为，以探索其应用。首次发现在芴单元的1-位和8-位上可以引入官能团。以3，6-二叔丁基芴为原料，在不同条件下进行氯甲基化反应，得到1，8-二（氯甲基）芴，再由1，8-二（氯甲基）芴经多步反应得到乙炔型芴。我们研究了从芴衍生物制备所需乙炔型大环化合物的各种方法。结果表明，以芴单元为基础的乙炔型大环化合物可以作为含有类似物的混合物合成。我们还引入了一个长的烷基链到芴单元的外部位置。用π-π方法研究了这些大环化合物的聚集行为。相互作用、氢键和静电相互作用。具有长烷基链的大环化合物在固态下显示出一些相。现在正在进行详细的研究，以澄清这些化合物的液晶特性。

Supramolecular chemistry which could produce novel functions by, combining small molecules using non-covalent bondings has always attracted a major interest. Macrocyclic compounds consisting of the acethylene units has the inner : cavity. Assembling these macrocyclic compounds, supramolecular structures such as a tube-like structure could be formed, which can be applied for host-guest chemistry and so forth. In this research we proposed the preparation of acethylene-type macrocyclic compounds based on the fluorene units instead of the benzene units and the examination of their aggregation behavior in order to explore the applications. We found out that some functional groups can be introduced into the 1-and 8-positions of the fluorene unit for the first time. Using 3,6-di-tert-butyl fluorene, chloromethylation was carried out under various conditions to give the 1,8-bis(chloromethyl)fluorene from which : the acethylene-type flourene was obtained in several steps. We have investigated various methods to prepare the desired acethylene-type macrocyclic compounds from the fluorene derivatives. As the result we could synthesize the acethylene-type macrocyclic compounds based on the fluorene units as the mixture which contains some analogous compound. We also introduce a long alkyl chain into the outer positions of the fluorene unit. Aggregation behavior of these macrocyclic compounds was investigated in terms of π-π. interaction, hydrogen-bondings and electrostatic interaction. The macrocyclic compounds having a long alkyl chain shows some phases in the solid state. Detail examination is now under way to clarify the liquid crystal properties of these compounds.