Pressure‐Induced Wide‐Range Reversible Emission Shift of Triphenylamine‐Substituted Anthracene via Hybridized Local and Charge Transfer (HLCT) Excited State,Advanced Optical Materials

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Pressure‐Induced Wide‐Range Reversible Emission Shift of Triphenylamine‐Substituted Anthracene via Hybridized Local and Charge Transfer (HLCT) Excited State
Advanced Optical Materials ( IF 8.0 ) Pub Date : 2017-12-21 , DOI: 10.1002/adom.201700647
Aisen Li _{1,

2} , Zhiyong Ma ₃ , Jinxia Wu ₁ , Ping Li ₁ , Hailong Wang ₁ , Yijia Geng ₁ , Shuping Xu ₁ , Bing Yang ₄ , Houyu Zhang ₁ , Haining Cui ₂ , Weiqing Xu ₁

Affiliation

4‐(Anthracen‐9‐yl)‐N,N‐diphenylaniline (TPA‐AN) is a typical molecule belonging to a donor–acceptor system. Here, the ordered crystal and the powder of TPA‐AN are used for high‐pressure Raman and fluorescence experiments, and their spectroscopic features under the shearing force of grinding and the hydrostatic pressure applied by a diamond anvil cell (DAC) are compared. The mechanochromism of TPA‐AN is discussed in detail based on the analysis of its single‐crystal structure and pressure‐driven spectral changes. During the DAC compression process, the TPA‐AN crystal shows an obvious emission band shift (from 476 to 600 nm) along with a new intramolecular charge transfer state that is separated from the hybridized local and charge transfer excited state and extremely sensitive to external force. Once the pressure is relieved, the Raman and fluorescence spectra both entirely self‐recover without a secondary force. To the authors' knowledge, TPA‐AN crystal is one of the largest emission shift organic mechanochromic fluorescent materials among reported publications. The reversible mechanochromic property of TPA‐AN for a wide‐range emission shift implies a great application potential as smart stimuli‐responsive layer in the fields of sensing, organic light‐emitting diode displays, and data storage.

中文翻译：

三苯胺取代的蒽经混合局部和电荷转移（HLCT）激发态的压力诱导的大范围可逆排放位移

4-（蒽-9-基）-N，N-二苯基苯胺（TPA-AN）是属于供体-受体系统的典型分子。在这里，将有序晶体和TPA-AN粉末用于高压拉曼和荧光实验，并比较了它们在磨削剪切力和金刚石砧座单元（DAC）施加的静水压力下的光谱特征。基于对TPA-AN的单晶结构和压力驱动的光谱变化的分析，详细讨论了TPA-AN的机械变色现象。在DAC压缩过程中，TPA-AN晶体显示出明显的发射带移（从476到600 nm）以及新的分子内电荷转移状态，该状态与杂化的局部和电荷转移激发态分开，并且对外力极为敏感。压力减轻后拉曼光谱和荧光光谱都可以完全自我恢复，而无需施加次级力。据作者所知，TPA-AN晶体是已报道出版物中最大的发射位移有机机械致变色荧光材料之一。TPA-AN的可逆机械变色特性可实现大范围的发射位移，这意味着它在传感，有机发光二极管显示器和数据存储领域作为智能刺激响应层具有巨大的应用潜力。

更新日期：2017-12-21

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