Structural Fluctuation of Disilanyl Double-Pillared Bisheteroarenes
Structural Fluctuation of Disilanyl Double-Pillared Bisheteroarenes
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DOI：
10.1002/asia.201300098
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发表时间：
2013-06-01
影响因子：
4.1
通讯作者：
Isobe, Hiroyuki
中科院分区：
文献类型：
--
作者：
Nakanishi, Waka;Shimada, Yusuke;Isobe, Hiroyuki
以三环杂芳烃为原料，采用一锅法合成了具有两个二硅烷基柱的硅环番。用X射线晶体学方法分析了三种含两个杂芳烃单元的同系物的单晶结构，发现它们具有阶梯状的反结构。根据芳族单元的结构，扭转角在二硅烷基柱改变，以保持整体的阶梯状分子结构。然而，该结构在溶液相中的反式和顺式构象之间波动，尽管环周边上存在8个甲基。用核磁共振光谱分析聚结温度显示了动力学的基本能量学。这种细微的结构差异影响了硅环番的动态行为。
Silacyclophanes possessing two disilanyl pillars were synthesized from tricyclic heteroarenes in one-pot synthetic procedures. The step-like anti structures of three congeners bearing two heteroarene units were revealed in single crystals by X-ray crystallographic analysis. Depending on the structures of aromatic units, torsion angles at the disilanyl pillars altered to maintain the overall step-like molecular structures. The structure, however, fluctuated between anti and syn conformers in a solution phase despite the presence of eight methyl groups on the ring periphery. The analysis of the coalescence temperature with NMR spectroscopy showed the fundamental energetics of the dynamics. The subtle structural differences affected the dynamic behavior of the silacyclophanes.