Synthesis of Bioctacene‐Incorporated Nanographene with Near‐Infrared Chiroptical Properties
Synthesis of Bioctacene‐Incorporated Nanographene with Near‐Infrared Chiroptical Properties
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具有近红外手性光学特性的生物并入纳米石墨烯的合成
DOI：
10.1002/anie.202218350
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Narita Akimitsu
中科院分区：
文献类型：
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作者：
Xu Xiushang;Munoz‐Marmol Rafael;Vasylevskyi Serhii;Villa Andrea;Folpini Giulia;Scotognella Francesco;Maria Paterno; Giuseppe;Narita Akimitsu
我们报道了具有两个并入的八苯亚结构的六苯并并六苯（HBPH）的合成，并通过单晶 X 射线分析明确地表征了该结构。 (P,P)-/(P,M)-形式的理论异构化势垒估计为38.4 kcal mol−1，并通过手性HPLC实现了分离。值得注意的是，对映体在近红外 (NIR) 区域（830nm）表现出相反的圆二色性响应，在 616nm 处的高 gabs 值为 0.017。此外，HBPH 表现出近红外发射，最大波长为 798 nm，绝对 PLQY 为 41 %。通过超快瞬态吸收光谱研究了 HBPH 的激发态光物理性质，揭示了一个有趣的特征，该特征归因于激发后 HBPH 的旋转和/或构象动力学。这些结果为具有近红外光学特性的手性纳米石墨烯的潜在手性光学应用的设计提供了新的见解。
We report the synthesis of a hexabenzoperihexacene (HBPH) with two incorporated octacene substructures, which was unambiguously characterized by single‐crystal X‐ray analysis. The theoretical isomerization barrier of the (P,P)‐/(P,M)‐forms was estimated to be 38.4 kcal mol−1, and resolution was achieved by chiral HPLC. Notably, the enantiomers exhibited opposite circular dichroism responses up to the near‐infrared (NIR) region (830 nm) with a highgabsvalue of 0.017 at 616 nm. Moreover, HBPH demonstrated NIR emission with a maximum at 798 nm and an absolute PLQY of 41 %. The excited‐state photophysical properties of HBPH were investigated by ultrafast transient absorption spectroscopy, revealing an intriguing feature that was attributed to the rotational and/or conformational dynamics of HBPH after excitation. These results provide new insight into the design of chiral nanographene with NIR optical properties for potential chiroptical applications.