Université d'Angers, CNRS UMR 6200, Laboratoire MOLTECH-Anjou, 2 bd Lavoisier, 49045 Angers (France), Fax: (+33) 02-41-73-54-05.
Chemistry. 2013 Sep 23;19(39):13160-7. doi: 10.1002/chem.201301095. Epub 2013 Aug 12.
Electroactive fused ethylenedithio-tetrathiafulvalene-[4]helicene and -[6]helicenes have been synthesized through a strategy that involved the preparation of 2,3-dibromo-helicene derivatives as intermediates. The dihedral angles between the terminal helicenes, as determined by single-crystal X-ray analysis, are 22.7° and 50.7° for the [4]helicene and [6]helicene, respectively. Their solid-state architectures show interplay between S⋅⋅⋅S and π⋅⋅⋅π intermolecular interactions. The chiroptical properties of the enantiopure EDT-TTF-[6]helicene derivatives have been investigated and supported by TDDFT calculations. Remarkable redox switching of the circular dichroism (CD) signal between the neutral and radical-cation species has been achieved.
通过一种涉及制备 2,3-二溴代螺旋烯衍生物作为中间体的策略，合成了电活性的融合乙撑二硫代四噻吩-[4]螺旋烯和-[6]螺旋烯。单晶 X 射线分析确定末端螺旋烯之间的二面角分别为 22.7°和 50.7°，用于[4]螺旋烯和[6]螺旋烯。它们的固态结构显示出 S⋅⋅⋅S 和 π⋅⋅⋅π 分子间相互作用的相互作用。对手性纯 EDT-TTF-[6]螺旋烯衍生物的手性光学性质进行了研究，并通过 TDDFT 计算得到了支持。在中性和自由基阳离子物种之间，圆二色性（CD）信号的显著氧化还原开关已经实现。
