Construction of novel unsaturated cyclophanes with π-cavitand structure

本论文设计合成了具有笼状结构的新型不饱和环番化合物，探索了六苯并[24]轮烯（Hexabenzo[24]annulene）的“自填充”结构，其中三个交替的芳烃环位于空腔内。这种能量最小的结构，在低温下观察到在溶液中，以及在固态。通过对不饱和δ-色氨酸的理论计算，发现该类化合物具有低还原电位和完全离域结构的电子性质.因此，许多方法的合成。化合物进行了检测。虽然没有实现合成，但已经开发了相关化合物的有效合成方法。这些方法也将应用于许多其他结构感兴趣的化合物，这些结果将为包括富勒烯在内的新型碳共轭体系的研究提供新的方向，这些碳共轭体系有望成为独特的纳米材料。

In this research, design and synthesis of novel unsaturated cyclophanes with caged structure was planned in order to investigate the unique electronic structure and to examine the possibility of the supramolecular chemistry based on the cavity surrounded with π-electrons.Hexabenzo[24]annulene, which is a macrocyclic benzannulene composed of six o-phenylenes and six cis-ethylene bridges, was probed to adopt a ‘self-filled' structure, where three alternate arene rings were located inside of the cavity. This energy-minimum structure was observed at low temperature in the solution as well as in the solid state. The preference of the conformer was ascribed to the cyclic concurrent CH-π interaction among the inside three benzene rings.Theoretical calculations for unsaturated deltaphanes, which was designed here, suggested the unique electronic properties : the compounds should have low reduction potential and the corresponding anions should have fully delocalized structure. Therefore, many methodologies for the synthesis of the. compounds were examined. Although the synthesis was not achieved, effective synthetic methods for the related compounds have been developed. These method will be applied for many other structurally interesting compounds.These results will provide new aspects for the research of new carbon conjugated systems including fullerenes, which are expected to be unique materials in nanotechnology applications.