Persistent, highly localized, and tunable [4]helicene radicals,Chemical Science

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Persistent, highly localized, and tunable [4]helicene radicals
Chemical Science ( IF 7.6 ) Pub Date : 2020-09-23 , DOI: 10.1039/d0sc04850j
Aslam C Shaikh ₁ , Jules Moutet ₁ , José M Veleta ₁ , Md Mubarak Hossain ₁ , Jan Bloch ₂ , Andrei V Astashkin ₁ , Thomas L Gianetti ₁

Affiliation

Persistent organic radicals have gained considerable attention in the fields of catalysis and materials science. In particular, helical molecules are of great interest for the development and application of novel organic radicals in optoelectronic and spintronic materials. Here we report the syntheses of easily tunable and stable neutral quinolinoacridine radicals under anaerobic conditions by chemical reduction of their quinolinoacridinium cation analogs. The structures of these [4]helicene radicals were determined by X-ray crystallography. Density functional theory (DFT) calculations, supported by electron paramagnetic resonance (EPR) measurements, indicate that over 40% of spin density is located at the central carbon of our [4]helicene radicals regardless of their structural modifications. The localization of the charge promotes a reversible oxidation to the cation upon exposure to air. This unusual reactivity toward molecular oxygen was monitored via UV-Vis spectroscopy.

中文翻译：

持久、高度局部化且可调节的[4]螺旋烯自由基

持久性有机自由基在催化和材料科学领域引起了相当大的关注。特别是，螺旋分子对于新型有机自由基在光电和自旋电子材料中的开发和应用引起了极大的兴趣。在这里，我们报道了在厌氧条件下通过化学还原其喹啉吖啶鎓阳离子类似物来合成易于调节且稳定的中性喹啉吖啶自由基。这些[4]螺烯自由基的结构通过X射线晶体学测定。由电子顺磁共振 (EPR) 测量支持的密度泛函理论 (DFT) 计算表明，超过 40% 的自旋密度位于我们的 [4]螺烯自由基的中心碳，无论其结构修饰如何。暴露于空气时，电荷的局部化促进了阳离子的可逆氧化。通过紫外-可见光谱监测这种对分子氧的不寻常反应。

更新日期：2020-09-23

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