Department of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Tokyo, 162-8601, Japan.
Chemistry. 2013 Apr 2;19(14):4513-24. doi: 10.1002/chem.201200716. Epub 2013 Feb 11.
The macrocyclization of 2,6-diethynyl hydrindacenes (1) with functional groups at mutually perpendicular positions results in the formation of novel macrocycles which, as a result of the hindered rotation of the hydrindacene units, possess directionally persistent peripheral functionalities. The two hydrindacene units in the dimer macrocycle (2) have been shown to interact electronically through their respective butadiyne moieties, whereas the trimer macrocycle (3) demonstrates a moderate degree of geometrical flexibility as a result of the five-membered hydrindacene rings. In addition, these trimer macrocycles contain a central cavity suitably sized for the inclusion of various solvent molecules. These new macrocycles can be further modified by introducing π-conjugated side groups, such as styryl and thienyl groups, as well as by attaching a variety of peripheral ester groups.
2,6-二乙炔基茚满（1）上相互垂直位置的官能团的大环化反应导致新型大环的形成，由于茚满单元的受阻旋转，这些大环具有定向持久的外围官能团。二聚体大环（2）中的两个茚满单元通过各自的丁二炔部分相互电子相互作用，而三聚体大环（3）由于五元茚满环的存在而具有一定程度的几何灵活性。此外，这些三聚体大环包含一个适合容纳各种溶剂分子的中心空腔。这些新的大环可以通过引入π共轭侧基（如苯乙烯基和噻吩基）以及连接各种外围酯基进一步修饰。
