Development of Novel Cyclic Structures Possessing Inclusion, Self-Assembly, and Self-Organization Properties

[l]含氢化茚并省骨架的新型受体的合成与性质氢化茚并省骨架由刚性的芳香环和柔性的五元环组成，通过引入合适的取代基可以有效地调控分子间的相互作用。本研究正是基于这一期望，对标题化合物的研究进行了探索，制备了几种取代的衍生物，并对其进行了X射线结构分析，结果表明：5元环的构象为包络构象，取代基（Rs）以约10 ~ 30的间距平行排列。7.0石墨层间距的两倍。这些结构特征被用来设计新型的多功能受体分子，这些分子优先与特定的底物结合。因此，（Z）Rs =芳基乙炔基/RL =烷氧羰基衍生物似乎在芳基乙炔基之间引入了芳香底物，这是通过π-π堆积相互作用促进的。还制备了Rs =烷氧羰基/R_L =芳基衍生物，并将其用于构建大环受体，其中前者的取代基位于环的内侧。[2]功能化亚苯基-亚乙炔基大环化合物的制备由DMAD和二氯乙烯经4步反应制得1，4-桥连二氯杜瓦苯。官能化的间-和对-亚苯基基团通过利用它们与弯曲的苯衍生物的等价性而方便地并入大环中。因此，它们与二乙炔基苯的交替（2：2）偶联-环化，然后水解和芳构化，提供了官能化的亚苯基-亚乙炔基大环，否则难以获得。

[l] Syntheses and Properties of Novel Receptors Possessing Hydrindacene Skeleton Hydrindacene skeleton is consisted of rigid central aromatic ring and flexible peripheral 5-membered rings, and its intermolecular interactions are expected to be adequately regulated by functionalizing those rings with suitable substituents. In this study, the development of title receptors was investigated on the basis of those expectations.The preparation of several substituted derivatives followed by their X-ray structural analyses revealed that the 5-membered rings prefer an envelope conformation and the less bulky substituents (Rs) are disposed nearly parallel to each other at a distance of ca. 7.0 Å, twice the interlayer distance in graphite. Those structural chacteristics were exploited to the design of novel multiply functionalized receptor molecules which preferentially associate with specific stubstrates. Thus, the (Z) Rs = arylethynyl/R_L = alkoxycarbonyl derivatives seem to incorporate aromatic substrates between the arylethynyl groups, facilitated by the π-π stacking interactions. The Rs = alkoxycarbonyl/R_L = aryl derivatives were also prepared and utilized to construct macrocyclic receptors in which the former substituents are oriented to the inside of the cycles.[2] Preparation of Functionalized Phenylene-ethynylene Macrocycles 1,4-Bridged dichloro-Dewar benzenes are accessible in 4 steps from DMAD and dichloroethylene. Functionalized m- and p-phenylene groups are conveniently incorporated into macrocycles by taking advantage of their equivalency to bent benzene derivatives. Thus, their alternating (2 : 2) coupling- cyclization with diethynylbenzenes followed by hydrolysis and aromatization provided functionalized phenylene-ethynylene macrocycles which were otherwise diffiucult to access.