Department of Chemistry, Tohoku University, Aoba-ku, Sendai, 980-8578, Japan.
Chem Asian J. 2011 Feb 1;6(2):554-9. doi: 10.1002/asia.201000543. Epub 2010 Oct 8.
A new series of silacyclophanes with two disilanyl pillars has been synthesized using a straightforward method. A silylation reaction of 1,8-dilithioanthracenes allowed the connection of two anthracene rings with two Si-Si bonds to afford disilanyl double-pillared bisanthracenes ((Si)DPBAs). The major product had an anti geometry of the anthracene rings, and a unique steplike structure favorable for σ-π conjugations was revealed by X-ray crystallographic analysis. Upon introducing a substituent at the 10-position of anthracene, we obtained a U-shaped isomer with syn geometry that yielded an excimer upon excitation and can decompose without steric protection.
已采用一种简单的方法合成了一系列具有两个二硅基支柱的新型硅杂环戊二烯。通过 1,8-二锂基蒽的硅烷化反应，可将两个蒽环与两个 Si-Si 键连接起来，得到二硅基双支柱双蒽((Si)DPBAs)。主要产物的蒽环具有反式几何构型，通过 X 射线晶体学分析揭示了一种独特的阶梯状结构，有利于 σ-π 共轭。在蒽的 10 位引入取代基后，我们得到了具有顺式几何构型的 U 型异构体，该异构体在激发时产生激基复合物，并且在没有空间位阻保护的情况下会分解。
