Lu Jinjie, Xia Aiyou, Zhou Nianchen, Zhang Wei, Zhang Zhengbiao, Pan Xiangqiang, Yang Yonggang, Wang Yong, Zhu Xiulin
Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application College of Chemistry, Chemical Engineering and Materials Science, Soochow University, No. 199, Ren'ai Road, Industrial Park, Suzhou 215123 (P.R. China).
Chemistry. 2015 Feb 2;21(6):2324-9. doi: 10.1002/chem.201405940. Epub 2014 Dec 15.
Two novel cyclic azobenzenophanes (SC, RC) with functional handles have been synthesized efficiently by a Glaser coupling reaction. Through a Suzuki coupling reaction, alternating ring/linear polymers with rigid (conjugated)/flexible (unconjugated) bridges were obtained from the resultant cyclic azobenzenophanes. The optical activities of linear, cyclic, and macromolecular binaphethyl-azobenzene derivatives were investigated by UV/Vis and circular dichroism (CD) spectra and the time-dependent (TD)-DFT method. Experimental results and theoretical analyses indicated that the cyclic configurations exhibited better chiroptical features than the others, and the reverse conformation and difference of dextro-/levo-rotation of azobenzenophanes were detected by comparing linear and cyclic structures, which provides an opportunity for the optical-rotation-controlled "smart" materials systems in future.
通过格拉泽偶联反应高效合成了两种带有功能基团的新型环状偶氮苯并菲（SC、RC）。通过铃木偶联反应，由所得的环状偶氮苯并菲制备出具有刚性（共轭）/柔性（非共轭）桥的交替环/线性聚合物。通过紫外/可见光谱和圆二色（CD）光谱以及含时密度泛函理论（TD-DFT）方法研究了线性、环状和大分子联萘基-偶氮苯衍生物的光学活性。实验结果和理论分析表明，环状构型比其他构型表现出更好的手性光学特性，通过比较线性和环状结构检测到了偶氮苯并菲的反向构象以及右旋/左旋旋转差异，这为未来的旋光控制“智能”材料系统提供了契机。
