Sakamaki Daisuke, Tanaka Shunya, Tanaka Katsuki, Takino Mayu, Gon Masayuki, Tanaka Kazuo, Hirose Takashi, Hirobe Daichi, Yamamoto Hiroshi M, Fujiwara Hideki
Department of Chemistry, Graduate School of Science, Osaka Prefecture University, Naka-ku, Sakai, Osaka 599-8531, Japan.
Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.
J Phys Chem Lett. 2021 Sep 30;12(38):9283-9292. doi: 10.1021/acs.jpclett.1c02896. Epub 2021 Sep 20.
Heterohelicenes are potential materials in molecular electronics and optics because of their inherent chirality and various electronic properties originating from the introduced heteroatoms. In this work, we comprehensively investigated two kinds of double NO-hetero[5]helicenes composed of 12-benzo[]phenoxazine () and 13-dibenzo[,]phenoxazine (). These helicenes exhibit good electron-donor properties reflecting the electron-rich character of their monomers and were demonstrated to work as p-type semiconductors. The enantiomers of these helicenes show the largest class of dissymmetry factors for circularly polarized luminescence (CPL) (|| > 10) among helicenes reported to date. Interestingly, the signs of CPL are opposite for and double helicenes of the same helicity. The origin of the large values and the inversion of the CPL sign was addressed by analysis of the transition electronic dipole moments and transition magnetic dipole moments based on TD-DFT calculations.
由于其固有的手性以及引入杂原子后产生的各种电子性质，杂螺旋烯是分子电子学和光学领域的潜在材料。在这项工作中，我们全面研究了由1,2-苯并[]吩恶嗪（）和1,3-二苯并[,]吩恶嗪（）组成的两种双NO-杂[5]螺旋烯。这些螺旋烯表现出良好的给电子性质，反映了其单体的富电子特性，并被证明可作为p型半导体。这些螺旋烯的对映体在迄今为止报道的螺旋烯中显示出最大类别的圆偏振发光（CPL）不对称因子（|| > 10）。有趣的是，相同螺旋度的和双螺旋烯的CPL符号相反。基于TD-DFT计算，通过分析跃迁电子偶极矩和跃迁磁偶极矩，探讨了大值的起源和CPL符号的反转。
