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

利用非共价键结合小分子产生新功能的超分子化学一直引起人们的极大兴趣。由乙烯单元组成的大环化合物具有内腔。将这些大环化合物组装在一起，可以形成管状结构等超分子结构，可应用于主客体化学等领域。本研究提出以芴基代替苯基制备乙炔型大环化合物，并对其聚集行为进行研究，以探索其应用前景。我们首次发现一些官能团可以被引入到芴单元的1位和8位上。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，并分步制得乙炔型芴。我们研究了从芴衍生物中制备乙炔型大环化合物的各种方法。结果表明，在含类似化合物的混合物中，可以合成基于芴单元的乙炔型大环化合物。我们还在芴单元的外部位置引入了一条长烷基链。用π-π来研究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体状态下显示出一些相。目前正在进行详细的研究，以阐明这些化合物的液晶性质。

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.