Tuning ESIPT fluorophores into dual emitters.
Tuning ESIPT fluorophores into dual emitters.
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DOI：
10.1039/c5sc04826e
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发表时间：
2016-06-01
期刊：
影响因子：
8.4
通讯作者：
Jacquemin D
中科院分区：
文献类型：
--
作者：
Azarias C;Budzák Š;Laurent AD;Ulrich G;Jacquemin D
使用第一性原理的方法，我们展示了如何ESIPT可以通过微调取代基，从而导致新的双发射器控制。染料分子在激发态发生分子内质子转移（ESIPT）时，由于光子吸收后的重要几何重组，会产生较大的斯托克斯位移。当ESIPT过程不是定量的时，可以获得双发射体，其特征在于两个不同的荧光带，由于来自正则异构体和ESIPT异构体的发射而观察到。然而，双发射通常需要保持非常特定的平衡，因为两种互变异构体的相对激发态自由能必须在窄窗口内才能观察到这种现象。因此，简单的化学直觉不足以优化双发射。在目前的贡献，我们调查，与量子力学工具的帮助下，更精确地说，含时密度泛函理论（TD-DFT）和代数图解建设（ADC），一个广泛的面板可能的ESIPT/双发射体与各种取代基。所选择的协议首先被证明是非常强大的一系列结构与已知的实验行为，然后被应用到新的衍生物与各种取代基位于不同的位置。这项工作包括迄今为止研究的潜在ESIPT化合物的最大化学库。我们确定了最有希望的组合，用于构建双发射器，突出了意想不到的组合效果，并合理化了不同助色剂的影响。
Using first-principle approaches, we show how ESIPT can be controlled by fine-tuning of substituents, hence leading to new dual emitters. Dyes undergoing excited-state intramolecular proton transfer (ESIPT) are known to present large Stokes shifts as a result of the important geometrical reorganisation following photon absorption. When the ESIPT process is not quantitative, one can obtain dual emitters characterised by two distinct fluorescence bands, observed due to emissions from both the canonical and ESIPT isomers. However, dual emission generally requires to maintain a very specific balance, as the relative excited-state free energies of the two tautomers have to be within a narrow window to observe the phenomenon. Consequently, simple chemical intuition is insufficient to optimise dual emission. In the present contribution, we investigate, with the help of quantum-mechanical tools and more precisely, time-dependent density functional theory (TD-DFT) and algebraic diagrammatic construction (ADC), a wide panel of possible ESIPT/dual emitters with various substituents. The selected protocol is first shown to be very robust on a series of structures with known experimental behaviour, and next is applied to novel derivatives with various substituents located at different positions. This work encompasses the largest chemical library of potential ESIPT compounds studied to date. We pinpoint the most promising combinations for building dual emitters, highlight unexpected combination effects and rationalise the impact of the different auxochromes.
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影响因子：
3.3
作者：
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