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轴向手性框架中用于窄深蓝光发射的增强圆二色活性:三维互锁结构

Enhanced chiroptical activity for narrow deep-blue emission in axial chiral frameworks three-dimensional interlocking.

作者信息

Mo Xuechao, Chen Guohao, Li Yulan, Xiao Biao, Chen Xuefeng, Yin Xiaojun, Yang Chuluo

机构信息

Shenzhen Key Laboratory of New Information Display and Storage Materials, College of Materials Science and Engineering, Shenzhen University Shenzhen 518060 P. R. China

出版信息

Chem Sci. 2024 Oct 5;15(42):17663-70. doi: 10.1039/d4sc05056h.

Abstract

The advancement of desirable circularly polarized luminescence (CPL) emitters is predominantly constrained by the effective regulation of magnetic and electric transition vectors, particularly within the deep-blue spectral domain. Herein, we present four pairs of novel chiral emitters with systematically varied molecular rigidity, symmetry, and chiral centers to elucidate the intrinsic coupling of key molecular parameters influencing their chiroptical properties. Notably, the incorporation of appropriate intramolecular 3D-interlocking within a natural binaphthyl chirality skeleton offers an effective approach to achieving both significantly narrowed full width at half maximum (FWHM, as low as 18 nm) and substantially enhanced chiroptical activity (luminous dissymmetry factor, , up to 3.0 × 10). Additionally, introducing a secondary chiral center closely parallel to the primary chiral plane facilitates strong chiral-chiral interactions, further affording a 50% improvement in their values. As a demonstration, vacuum-deposited circularly polarized organic light-emitting diodes incorporating these pure fluorescent emitters exhibit outstanding electroluminescent performance, with maximum external quantum efficiency exceeding 5.35%, favorable FWHM of approximately 25 nm, and extreme CIE values below 0.03.

摘要

理想的圆偏振发光(CPL)发射体的发展主要受到磁跃迁和电跃迁矢量有效调控的限制,尤其是在深蓝色光谱区域。在此,我们展示了四对具有系统变化的分子刚性、对称性和手性中心的新型手性发射体,以阐明影响其手性光学性质的关键分子参数的内在耦合。值得注意的是,在天然联萘手性骨架内引入适当的分子内三维互锁提供了一种有效方法,可实现半高宽(FWHM,低至18 nm)显著变窄和手性光学活性大幅增强(发光不对称因子,高达3.0×10)。此外,引入与主手性平面紧密平行的二级手性中心有助于增强手性 - 手性相互作用,进一步使其值提高50%。作为示例,包含这些纯荧光发射体的真空沉积圆偏振有机发光二极管表现出出色的电致发光性能,最大外量子效率超过5.35%,半高宽约为25 nm,且色坐标(CIE)值极低,低于0.03。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d63a/11526136/4fd9cd6371de/d4sc05056h-s1.jpg

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