Kai Nobushige, Kono Hideya, Stünkel Timo, Imoto Daiki, Zanasi Riccardo, Monaco Guglielmo, Summa Francesco F, Scott Lawrence T, Yagi Akiko, Itami Kenichiro
Department of Chemistry, Graduate School of Science, Nagoya University Chikusa Nagoya 464-8602 Japan
Dipartimento di Chimica e Biologia "A. Zambelli", Università Degli Studi di Salerno Fisciano 84084 SA Italy
Chem Sci. 2025 Apr 23. doi: 10.1039/d5sc01305d.
Nanobelts are cyclic arenes that only consist of annulated structures. Recently, various types of nanobelts have been synthesized and their unique properties have been unveiled. However, cationic nanobelts without heteroatoms have been rarely synthesized, and their properties are of significant interest from both fundamental and application perspectives. Herein, we report the synthesis of radical cationic and dicationic hydrocarbon nanobelts by chemical oxidation of methylene-bridged [6]cycloparaphenylene ([6]MCPP). These cationic species are remarkably stable in air, which made it possible to measure and uncover their structural and electronic properties. Notably, the [6]MCPP dicationic salt has sharp absorption and fluorescence bands at longer wavelengths than those of neutral [6]MCPP, close to the near-infrared region. From both experimental and theoretical investigation, the existence of a strong diatropic belt current in [6]MCPP dication was indicated. In addition, a longer lifetime was observed for the hexamethyl[6]MCPP dicationic salt than for the [6]MCPP dicationic salt in solution.
纳米带是仅由环化结构组成的环状芳烃。最近,已合成了各种类型的纳米带,并揭示了它们的独特性质。然而,不含杂原子的阳离子纳米带很少被合成,并且从基础和应用的角度来看,它们的性质都引起了极大的兴趣。在此,我们报告了通过亚甲基桥连的[6]环对亚苯基([6]MCPP)的化学氧化合成自由基阳离子和二价阳离子碳氢化合物纳米带。这些阳离子物种在空气中非常稳定,这使得测量和揭示它们的结构和电子性质成为可能。值得注意的是,[6]MCPP二价阳离子盐在比中性[6]MCPP更长的波长处有尖锐的吸收和荧光带,接近近红外区域。通过实验和理论研究均表明,[6]MCPP二价阳离子中存在强抗磁带电流。此外,在溶液中观察到六甲基[6]MCPP二价阳离子盐的寿命比[6]MCPP二价阳离子盐更长。
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