由同手性端功能化螺旋烯组成的永久极性的面对面螺旋柱。

IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Zheng Zhang, Weizhe Hu, Zhibo Liu, Yusuke Tsutsui, Yasujiro Murata, Shu Seki and Takashi Hirose*, 
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引用次数: 0

摘要

手性π共轭分子在自旋选择性有机半导体和响应圆偏振光的手性电子器件中具有很大的应用潜力。预计它们的性能将受到它们在固态中如何组装的强烈影响。然而,控制填充结构的策略,特别是在螺旋扭曲π共轭分子中,仍然有限。在这项工作中,我们通过用2,1,3-噻二唑和菲的环结构修饰螺旋衍生物的螺旋末端,实现了螺旋衍生物的同手性面对面柱状排列。理论计算表明,在面对面的柱状排列中,分子间相互作用明显强(例如,Etotal = -113.9 kJ·mol-1),与在平面π共轭分子中观察到的相互作用相当,这可能是由于相邻螺旋分子之间的大重叠区域。噻二唑-熔融衍生物(P)-TD b[7]H和菲二唑-熔融衍生物(M)-1在固态中呈面对面柱状排列,通过闪烁光解时间分辨微波电导率法测定,其光电导率最大值为ΦΣμmax = 1 × 10-5 cm2·V-1·s-1,证实了其作为有机半导体的潜力。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Face-to-Face Helical Columns with Permanent Polarity Consisting of Homochiral End-Functionalized Helicenes

Face-to-Face Helical Columns with Permanent Polarity Consisting of Homochiral End-Functionalized Helicenes

Chiral π-conjugated molecules hold great potential for applications in spin-selective organic semiconductors and chiroptical electronic devices that respond to circularly polarized light. Their performance is anticipated to be strongly influenced by how they assemble in the solid state. However, strategies for controlling the packing structure─particularly in helically twisted π-conjugated molecules─remain limited. In this work, we achieved a homochiral face-to-face columnar packing arrangement for helicene derivatives by modifying their helical ends with 2,1,3-thiadiazole and phenanthrene-fused ring structures. Theoretical calculations suggested significantly strong intermolecular interactions in the face-to-face columnar arrangement (e.g., Etotal = −113.9 kJ·mol–1), comparable to those observed in planar π-conjugated molecules, likely due to the large overlap area between adjacent helical molecules. Thiadiazole-fused derivative (P)-TD[7]H and phenanthrene-fused derivative (M)-1, with face-to-face columnar arrangements in the solid state, exhibited a photoconductivity maximum of ΦΣμmax = 1 × 10–5 cm2·V–1·s–1 as determined by the flash-photolysis time-resolved microwave conductivity method, confirming its potential as an organic semiconductor.

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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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