[2,2](5,8)Picenophanedienes: Syntheses, Structural Analyses, Molecular Dynamics, and Reversible Intramolecular Structure ConversionClick to copy article linkArticle link copied!
- Min-Chih TangMin-Chih TangDepartment of Chemistry, National Cheng Kung University, 70101 Tainan, TaiwanMore by Min-Chih Tang
- Yu-Chen WeiYu-Chen WeiDepartment of Chemistry, National Taiwan University, 10617 Taipei, TaiwanMore by Yu-Chen Wei
- Yen-Chen ChuYen-Chen ChuDepartment of Chemistry, National Cheng Kung University, 70101 Tainan, TaiwanMore by Yen-Chen Chu
- Cai-Xin JiangCai-Xin JiangDepartment of Chemistry, National Cheng Kung University, 70101 Tainan, TaiwanMore by Cai-Xin Jiang
- Zhi-Xuan HuangZhi-Xuan HuangDepartment of Chemistry, National Taiwan University, 10617 Taipei, TaiwanMore by Zhi-Xuan Huang
- Chi-Chi WuChi-Chi WuDepartment of Chemistry, National Taiwan University, 10617 Taipei, TaiwanMore by Chi-Chi Wu
- Tzu-Hsuan ChaoTzu-Hsuan ChaoDepartment of Chemistry, National Cheng Kung University, 70101 Tainan, TaiwanMore by Tzu-Hsuan Chao
- Pei-Hsun HongPei-Hsun HongDepartment of Chemistry, National Cheng Kung University, 70101 Tainan, TaiwanMore by Pei-Hsun Hong
- Mu-Jeng Cheng*Mu-Jeng Cheng*[email protected]Department of Chemistry, National Cheng Kung University, 70101 Tainan, TaiwanMore by Mu-Jeng Cheng
- Pi-Tai Chou*Pi-Tai Chou*[email protected]Department of Chemistry, National Taiwan University, 10617 Taipei, TaiwanMore by Pi-Tai Chou
- Yao-Ting Wu*Yao-Ting Wu*[email protected]Department of Chemistry, National Cheng Kung University, 70101 Tainan, TaiwanMore by Yao-Ting Wu
Abstract
This study presents an important and efficient synthetic approach to 5,8-dibromo-2,11-di-tert-butylpicene (3), with multigram scale, which was then converted to a new series of picenophanes (6–10). The tub-shaped [2,2](5,8)picenophanediene 8 with two cis-ethylene linkers was explored using X-ray crystallography. The tub-to-tub inversion proceed through the successive bending of the linkers and the barrier for isopropyl-substituted derivative 10 was experimentally estimated to be 18.7 kcal/mol. Picenophanes with a large π-system and semi-rigid structure exhibited anomalous photophysical properties. The ethano-bridged picenophane shows the weak exciton delocalization while the cis-ethylene-bridged picenophane exhibits dual emission rendered by the weakly delocalized exciton and excimer. With the aid of the ultrafast time-resolved emission spectroscopy, the mechanism of the excimer formation is resolved, showing a unique behavior of two-state reversible reaction with fast structural deformation whose lifetime is around 20 ps at 298 K. This work demonstrates that the slight difference in the bridge of tub-shaped picenophanes renders distinct photophysical behavior, revealing the potential of harnessing inter-moiety reaction in the picenophane systems.
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