Axially Chiral Spiro-conjugated Carbon-bridged p-Phenylenevinylene Congeners: Synthetic Design and Materials Properties,Journal of the American Chemical Society

当前位置： X-MOL 学术 › J. Am. Chem. Soc. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Axially Chiral Spiro-conjugated Carbon-bridged p-Phenylenevinylene Congeners: Synthetic Design and Materials Properties
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-01-10 , DOI: 10.1021/jacs.9b13019
Hiroyoshi Hamada ₁ , Yuki Itabashi ₁ , Rui Shang ₁ , Eiichi Nakamura ₁

Affiliation

Spiro-conjugated systems are attracting considerable interest for their chiroptical properties, and because of their compact structure, the small reorganization energy upon electronic excitation or ionization. We report here a modular and convergent synthesis of axially chiral spiro-conjugated carbon-bridged p-phenylenevinylenes (spiro-CPVs) in a racemic and optically active form where two carbon-bridged p-phenylenevinylene molecules are connected by a spiro carbon atom. Our synthetic design focuses on the C2 symmetry of the spiro-CPV molecules, relying on coupling of two 3-lithio-2-arylindene molecules on a carbon monooxide molecule that serves as the spiro carbon center in the target molecule. We prepared derivatives including those possessing phenol groups that facilitate optical resolution and also serve as a platform for the synthesis of a variety of optically active derivatives, which exhibit circularly polarized photoluminescence with high fluorescence quantum yields, large dissymmetry factors, and high photostability. For example, a bis(phenylethynyl) derivative exhibited a fluorescence quantum yield of 0.99, and a dissymmetry factor in luminescence of |glum| = 2.7 × 10-4, values highest among, and comparable to those of reported CPL compounds, respectively. A tetrakis-diarylamine derivative shows hole mobility (μh = 3.84 × 10-5 cm2 V-1 s-1; space charge limited current measurement of a spin-coated film) comparable to that of a popularly used hole-transporting material, spiro-OMeTAD (μh = 2.6 ×10-5 cm2 V-1 s-1), as well as high thermal and phase stability (T5d = 382 °C, Tg = 171 °C).

中文翻译：

轴向手性螺共轭碳桥联对苯乙炔同系物：合成设计和材料特性

螺共轭系统因其手性光学特性而引起了相当大的兴趣，并且由于其结构紧凑，电子激发或电离时的重组能很小。我们在此报告了外消旋和光学活性形式的轴向手性螺共轭碳桥联对亚苯基亚乙烯基 (spiro-CPV) 的模块化和收敛合成，其中两个碳桥联对亚苯基亚乙烯基分子通过螺碳原子连接。我们的合成设计侧重于螺环 CPV 分子的 C2 对称性，依赖于两个 3-lithio-2-arylindene 分子与作为目标分子中螺碳中心的一氧化碳分子的偶联。我们制备了衍生物，包括那些具有促进光学分辨率的苯酚基团的衍生物，并作为合成各种光学活性衍生物的平台，这些衍生物表现出圆偏振光致发光，具有高荧光量子产率、大不对称因子和高光稳定性。例如，双(苯乙炔基)衍生物的荧光量子产率为0.99，发光不对称因子为|glum|。= 2.7 × 10-4，分别是所报道的 CPL 化合物中最高的值，并且与这些值相当。四二芳基胺衍生物的空穴迁移率（μh = 3.84 × 10-5 cm2 V-1 s-1；旋涂膜的空间电荷限制电流测量）与常用的空穴传输材料螺- OMeTAD（μh = 2.6 ×10-5 cm2 V-1 s-1），

更新日期：2020-01-10

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11