Spiro-functionalized Diphenylethenes: Suppression of a Reversible Photocyclization Contributes to the AIE Effect,Journal of the American Chemical Society

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Spiro-functionalized Diphenylethenes: Suppression of a Reversible Photocyclization Contributes to the AIE Effect
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-06-16 , DOI: 10.1021/jacs.9b04426
Zhibiao Zhou ₁ , Sheng Xie ₂ , Xian Chen ₁ , Yujie Tu ₂ , Jiannan Xiang ₁ , Jianguo Wang _{2,

3} , Zikai He ₄ , Zebing Zeng ₁ , Ben Zhong Tang _{2,

5}

Affiliation

Many aggregation-induced emission (AIE) materials are featured by the diphenylethene (DPE) moiety which exhibits rich photophysical and photochemical activities. The understanding of these activities behind AIE is essential to guide the design of fluorescent materials with improved performance. Herein by fusing a flexible DPE with a rigid spiro scaffold, we report a class of novel deep-blue material with solid-state fluorescent quantum yield (ΦF) up to 99.8%. Along with the AIE phenomenon, we identified a reversible photocyclization (PC) on DPE with visible chromism, which is, on the contrary, popularized in solutions but blocked by aggregation. We studied the steric and electronic effects of structural perturbation and concluded that the PC is a key process behind the RIMs (restriction of intramolecular motions) mechanism for these materials. Mitigation of the PC leads to enhanced fluorescence in solutions and loss of the AIE characteristics.

中文翻译：

螺功能化二苯乙烯：抑制可逆光环化有助于 AIE 效应

许多聚集诱导发射 (AIE) 材料的特点是二苯乙烯 (DPE) 部分表现出丰富的光物理和光化学活性。了解 AIE 背后的这些活动对于指导具有改进性能的荧光材料的设计至关重要。在本文中，通过将柔性 DPE 与刚性螺支架融合，我们报告了一类具有高达 99.8% 的固态荧光量子产率 (ΦF) 的新型深蓝色材料。随着 AIE 现象，我们在 DPE 上发现了一种可逆的光环化 (PC)，具有可见的变色，相反，它在溶液中普及，但被聚集阻止。我们研究了结构扰动的空间和电子效应，并得出结论，PC 是这些材料的 RIM（分子内运动限制）机制背后的关键过程。

更新日期：2019-06-16

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