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调控激发态手性以制备高性能固态圆偏振发光材料。

Regulating the excited state chirality to fabricate high-performance-solid-state circularly polarized luminescence materials.

作者信息

Han Jianlei, Shi Yonghong, Jin Xue, Yang Xuefeng, Duan Pengfei

机构信息

CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology (NCNST) No. 11 ZhongGuanCun BeiYiTiao Beijing 100190 P. R. China

University of Chinese Academy of Sciences Beijing 100049 P. R. China.

出版信息

Chem Sci. 2022 Apr 27;13(20):6074-6080. doi: 10.1039/d2sc01846b. eCollection 2022 May 25.

Abstract

Developing solid-state materials and greatly improving the luminescence dissymmetry factors ( ) are the key issues for the future oriented practical application in the field of circularly polarized luminescence (CPL). However, most of the solid-state CPL-active materials suffer from aggregation caused emission quenching and relatively small values, which intensively restrict the development and application. In this work, high-performance CPL-active solid-state materials were achieved by regulating the excited state chirality of a series of bi-pyrene based chiral emitters. Due to the reversible mechanochromic luminescence under external stimuli, their excited state chirality can also be switched. It was found that the pristine amorphous powder possessed weak but obvious chiroptical properties because of the inherently chiral structures. Mechanical grinding could switch the fluorescence color and eliminate the CPL activity. Subsequently, by carrying out solvent fumigation, instant crystallization with well-defined microcrystal formation occurred, which could activate the CPL emission. Due to the chiral supramolecular arrangement of chromophores in the crystalline state, the resulting excimer emission in microcrystals showed chirality amplification not only in the excited state but also in the ground state. These findings not only provide a new method to fabricate high-performance CPL-active solid-state materials, but also clarify the chirality origin of pyrene-excimer-based chiral luminophores in various states which showed the importance of CPL as a probe of excited state chirality.

摘要

开发固态材料并大幅提高发光不对称因子( )是圆偏振发光(CPL)领域未来实际应用的关键问题。然而,大多数固态CPL活性材料存在聚集导致的发光猝灭以及相对较小的 值,这严重限制了其发展和应用。在这项工作中,通过调节一系列基于联芘的手性发光体的激发态手性,获得了高性能的CPL活性固态材料。由于在外部刺激下具有可逆的机械变色发光,它们的激发态手性也可以切换。研究发现,原始的无定形粉末由于其固有的手性结构而具有微弱但明显的手性光学性质。机械研磨可以切换荧光颜色并消除CPL活性。随后,通过进行溶剂熏蒸,发生了具有明确微晶形成的即时结晶,这可以激活CPL发射。由于发色团在结晶状态下的手性超分子排列,微晶中产生的准分子发射不仅在激发态而且在基态都表现出手性放大。这些发现不仅提供了一种制备高性能CPL活性固态材料的新方法,还阐明了基于芘准分子的手性发光体在各种状态下的手性起源,这表明CPL作为激发态手性探针的重要性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7015/9132027/2f9fe0c5bf5f/d2sc01846b-f1.jpg

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