Theoretical insights into excited‐state process for the novel 2,3‐bis[(4‐diethylamino‐2‐hydroxybenzylidene)amino]but‐2‐enedinitrile system,Journal of the Chinese Chemical Society

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Theoretical insights into excited‐state process for the novel 2,3‐bis[(4‐diethylamino‐2‐hydroxybenzylidene)amino]but‐2‐enedinitrile system
Journal of the Chinese Chemical Society ( IF 1.6 ) Pub Date : 2019-07-29 , DOI: 10.1002/jccs.201900202
Lei Xu ₁ , Tianjie Zhang ₁ , Dapeng Yang _{1,

2} , Qiaoli Zhang ₁

Affiliation

In this present work, we clarify the excited‐state intramolecular proton transfer (ESIPT) mechanism for 2,3‐bis[(4‐diethylamino‐2‐hydroxybenzylidene)amino]but‐2‐enedinitrile (BDABE) system. We present the fact that excited‐state single proton transfer can occur along with one hydrogen bond, even though BDABE form consists of two intramolecular hydrogen bonds. Based on the density functional theory and time‐dependent density functional theory methods, we theoretically investigate and elaborate the excited‐state intramolecular dual hydrogen‐bonding interactions. By simulating the electrostatic potential surface, we verify the formation of dual intramolecular hydrogen bonds for BDABE molecule in the S₀ state. Furthermore, comparing the primary bond lengths and bond angles as well as the infrared vibrational spectra, we find that the double hydrogen bonds should be strengthened in the S₁ state. When it comes to photoexcitation process, we discover the charge redistribution around hydrogen bonding moieties. The increased electronic density around proton acceptor plays the important roles in strengthening hydrogen bonds and in facilitating ESIPT reaction. In view of the possible ESIPT reaction paths (i.e., stepwise and synchronization double proton transfer) for BDABE molecule, we explored the S₀‐state and S₁‐state potential energy curves. This work explains experimental results and further clarifies the excited‐state behaviors for BDABE system.

中文翻译：

新型2,3-双[（4-二乙基氨基-2-羟基亚苄基）氨基]但是-2-烯键式杀菌体系的激发态过程的理论见解

在本工作中，我们阐明了2,3-双[（4-二乙基氨基-2-羟基苄叉基）氨基]但是-2-烯键化（BDABE）系统的激发态分子内质子转移（ESIPT）机制。我们提出了一个事实，即使BDABE形式由两个分子内氢键组成，激发态的单个质子转移也可能与一个氢键一起发生。基于密度泛函理论和时变密度泛函理论方法，我们从理论上研究和阐述了激发态分子内双氢键相互作用。通过模拟静电势表面，我们验证了S _0中BDABE分子的双分子内氢键的形成状态。此外，通过比较主键长度和键角以及红外振动光谱，我们发现在S ₁状态下应加强双氢键。当涉及到光激发过程时，我们发现氢键部分周围的电荷重新分布。质子受体周围电子密度的增加在加强氢键和促进ESIPT反应中起着重要作用。鉴于BDABE分子可能存在的ESIPT反应路径（即逐步和同步双质子转移），我们探索了S ₀状态和S ₁状态势能曲线。这项工作解释了实验结果，并进一步阐明了BDABE系统的激发态行为。

更新日期：2020-02-14

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