用笨重的手性帽包裹三芳基三嗪:通过分子旋转调节固态智光学特性的发光手性晶体分子旋转体

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Namhee Kim, Pingyu Jiang, Ryunosuke Tomita, Ayana Sato-Tomita, Alexander S. Mikherdov, Byeong-Su Kim and Mingoo Jin*, 
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引用次数: 0

摘要

本文介绍了发光手性晶体分子转子的一种新型结构模式,它具有与晶体介质中旋转运动相关的自旋特性。通过单晶 X 射线衍射 (XRD) 分析证实,这种支架将由带有三异丙基硅烷基 (TIPS) 的同手性二萘基分子组成的笨重手性帽与三芳基三嗪结合在一起。变温固态 2H NMR 研究表明,在 263 至 333 K 之间,转子晶体中的亚苯基发生了 4 倍旋转,而立体转子类似物则没有旋转运动。值得注意的是,在手性转子中观察到加热时二萘基的二面角减小,并在固态中检测到相应的圆二色性(CD)信号变化,而立体转子的二面角没有因温度变化而改变。我们认为,苯基环的快速旋转会影响邻近异丙基的运动,导致与二萘基的立体排斥,从而引起其构象变化。此外,手性转子在固态低温下表现出圆极化磷光,这是由于三苯基三嗪在激发态结构弛豫过程中苯基发生了旋转位移。同时,立体转子在激发态下通过立体阻碍的晶格环境抑制分子运动,从而显示出明显的圆极化荧光。这些结果表明,三芳基三嗪中引入的笨重手性帽作为发光的手性结晶分子转子,可以成为通过分子旋转运动调节固态光电性质的有用支架。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Encasing Triaryltriazine with a Bulky Chiral Cap: Luminescent Chiral Crystalline Molecular Rotors with Modulation of Solid-State Chiroptical Properties Mediated by Molecular Rotation

Encasing Triaryltriazine with a Bulky Chiral Cap: Luminescent Chiral Crystalline Molecular Rotors with Modulation of Solid-State Chiroptical Properties Mediated by Molecular Rotation

A novel structural motif for luminescent chiral crystalline molecular rotors with chiroptical properties correlated with the rotational motion in crystalline media is presented. This scaffold incorporates bulky chiral caps consisting of a homochiral binaphthyl moiety with a triisopropylsilyl (TIPS) group into triaryltriazine, as confirmed by single-crystal X-ray diffraction (XRD) analysis. Variable-temperature solid-state 2H NMR studies revealed a 4-fold rotation of the phenylenes occurred in the rotor crystal between 263 and 333 K, while a steric rotor analogue shows no rotational motion. Notably, a reduction in the dihedral angle of the binaphthyl moiety upon heating was observed in the chiral rotors, and a corresponding alteration of the circular dichroism (CD) signal was detected in the solid-state, while those of the steric rotors showed no alteration by the temperature change. We propose that the fast rotation of the phenyl rings affects the motion of neighboring isopropyl groups, leading to steric repulsion with the binaphthyl moieties and thereby inducing its conformational change. Furthermore, the chiral rotors exhibited circularly polarized phosphorescence in the solid-state at low temperature, originating from rotational displacement of the phenylene on triphenyltriazine during structural relaxation in the excited state. Meanwhile, the steric rotors showed significant circularly polarized fluorescence induced by the suppressed molecular motion via a sterically hindered lattice environment in the excited state. These results indicate that the bulky chiral cap introduced into the triaryltriazines, acting as a luminescent chiral crystalline molecular rotor, can be a useful scaffold for the modulation of solid-state chiroptical properties via molecular rotational motions.

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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
期刊介绍: The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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