Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany.
J Am Chem Soc. 2013 Feb 13;135(6):2160-3. doi: 10.1021/ja400416r. Epub 2013 Jan 30.
Influencing the communication within a conjugated system as diphenylacetylene is a challenging subject in molecular electronics. Some examples of twisted tolanes are known, where high twists have been achieved in the solid state by steric encumbrance. The insertion of a spacer system is an alternative way to tailor rotation. Only a few examples of such tethered tolanes exist, and they all suffer from small twist angles (<35°). We report on tolanophanes containing a malonyl tether, where twist angles of almost 80° were reached. Long-lived phosphorescence (4 s at 77 K) was recorded, and quantum-chemical calculations were performed to confirm the experimental results.
在共轭体系中二苯乙炔的影响是分子电子学中一个具有挑战性的课题。已知一些扭曲的噻吩的例子，在固态中通过空间位阻实现了高扭曲度。插入间隔系统是调整旋转的另一种方法。只有少数这样的键合噻吩的例子存在，而且它们的扭转角度都很小（<35°）。我们报告了含有丙二酰基键的噻吩烷，其扭转角度接近 80°。记录到了长寿命磷光（77 K 时为 4 s），并进行了量子化学计算以验证实验结果。
