Wu Yin-Fu, Ying Si-Wei, Liao Song-Di, Zhang Ling, Du Jun-Jie, Chen Bin-Wen, Tian Han-Rui, Xie Fang-Fang, Xu Han, Deng Shun-Liu, Zhang Qianyan, Xie Su-Yuan, Zheng Lan-Sun
State Key Laboratory for Physical Chemistry of Solid Surfaces, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), Department of Chemistry, Xiamen University, Xiamen, 361005, China.
Angew Chem Int Ed Engl. 2022 Aug 15;61(33):e202204334. doi: 10.1002/anie.202204334. Epub 2022 Jul 4.
Herein, a hetero(S,N)-quintuple [9]helicene (SNQ9H) molecule with an azacorannulene core was synthesized, currently representing the highest hetero-helicene reported in the field of multiple [n]helicenes. X-ray crystallography indicated that SNQ9H includes not only a propeller-shaped conformer SNQ9H-1, but also an unforeseen quasi-propeller-shaped conformer SNQ9H-2. Different conformers were observed for the first time in multiple [n≥9]helicenes, likely owing to the doping of heteroatomic sulfurs in the helical skeletons. Remarkably, the ratio of SNQ9H-1 to SNQ9H-2 can be regulated in situ by the reaction temperature. Experimental studies on the photophysical and redox properties of SNQ9H and theoretical calculations clearly demonstrated that the electronic structures of SNQ9H depend on their molecular conformations. The strategy of introducing heteroatomic sulfurs into the helical skeleton may be useful in constructing various conformers of higher multiple [n]helicenes in the future.
在此，合成了一种具有氮杂蒄核心的杂（S，N）-五元[9]螺旋烯（SNQ9H）分子，它是目前多[n]螺旋烯领域报道的最高级杂螺旋烯。X射线晶体学表明，SNQ9H不仅包含螺旋桨形状的构象异构体SNQ9H-1，还包含一种意外的准螺旋桨形状的构象异构体SNQ9H-2。在多个[n≥9]螺旋烯中首次观察到不同的构象异构体，这可能是由于螺旋骨架中杂原子硫的掺杂。值得注意的是，SNQ9H-1与SNQ9H-2的比例可以通过反应温度原位调节。对SNQ9H的光物理和氧化还原性质的实验研究以及理论计算清楚地表明，SNQ9H的电子结构取决于其分子构象。将杂原子硫引入螺旋骨架的策略可能在未来构建各种更高阶多[n]螺旋烯的构象异构体方面有用。
