Laterally π-Extended Dithia[6]helicenes with Heptagons: Saddle-Helix Hybrid Molecules
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- Yasutomo Segawa
- JST, ERATO, Itami Molecular Nanocarbon Project, Chikusa, Nagoya 464-8602, Japan
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- Kenichiro Itami
- JST, ERATO, Itami Molecular Nanocarbon Project, Chikusa, Nagoya 464-8602, Japan
書誌事項
- 公開日
- 2017-07-12
- 資源種別
- journal article
- DOI
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- 10.1021/acs.joc.7b01540
- 公開者
- American Chemical Society (ACS)
この論文をさがす
説明
A laterally π-extended dithia[6]helicene 1, representing an interesting saddle-helix hybrid molecule containing an unusual heptagon, has been synthesized by MoCl5-mediated oxidative stitching of tetrakis(thienylphenyl)naphthalene precursor 2 involving reactive-site capping by chlorination and subsequent Pd-mediated dechlorination of tetrachlorinated intermediate 1-Cl4. Highly distorted, wide helical structures of dithia[6]helicenes (1 and 1-Cl4) were clarified by single-crystal X-ray diffraction analyses where heterochiral slipped π-π stacking was displayed in a one-dimensional fashion. Notably, theoretical studies on the thermodynamic behavior of 1 predicted an extraordinarily high isomerization barrier of 49.7 kcal·mol-1, which enabled optical resolution and chiroptical measurements. Electronic structures of these huge helicenes were also examined by photophysical and electrochemical measurements.
収録刊行物
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- The Journal of Organic Chemistry
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The Journal of Organic Chemistry 82 (15), 7745-7749, 2017-07-12
American Chemical Society (ACS)
