Pyrene-Containing Twistarene: Twelve Benzene Rings Fused in a Row
Pyrene-Containing Twistarene: Twelve Benzene Rings Fused in a Row
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DOI：
10.1002/anie.201808779
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发表时间：
2018-10-08
影响因子：
16.6
通讯作者：
Zhang, Qichun
中科院分区：
文献类型：
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作者：
Chen, Wangqiao;Li, Xinxiong;Zhang, Qichun
成功获得具有精确结构的高阶扭转芳烃对于从根本上理解结构与物理性质/光电应用之间的关系非常重要。在本研究中，利用反diels - alder工艺（清洁反应）的优点和芘单元的交叉共轭性质，首次制备了一种新型十二扭芳烃。单晶XRD分析证实，其结构具有一个扭曲角（约30度），由于其扭曲特性和分子间强的CH-pi相互作用，晶格中相邻的两个分子相互垂直。然而，它的基本物理化学性质表明，它在空气中的不稳定性源于其HOMO能级的升高，尽管NICS计算证实，芘单位对整个分子的共轭作用很小。
Success in obtaining higher-order twistarenes with precise structures is very important for fundamentally understanding the relationship between the structures and physical properties/optoelectronic applications. In this research, by using the advantages from a retro-Diels-Alder process (clean reaction) and the cross-conjugated nature of the pyrene unit, a novel dodeca-twistarene was prepared for the first time. Its structure, confirmed by single-crystal XRD analysis, indicates that it possesses a twisted angle (approximate to 30 degrees), and two neighboring molecules in the crystal lattice are perpendicular to each other because of the twisted character and the strong intermolecular CH-pi interactions. However, its basic physicochemical properties suggest its instability in air derives from its elevated HOMO energy level, although NICS calculations confirm that the pyrene units contribution poorly to the conjugation of the overall molecule.