Insights into the photoinduced anion translocation of the Donor-π-Acceptor+(ion)- molecules

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Hao-Ting Qu, Iida Partanen, Kai-Hsin Chang, Yan-Ding Lin, Igor O Koshevoy, Andrey Belyaev, Pi-Tai Chou
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引用次数: 0

Abstract

By strategic design and synthesis of a new series of phosphonium salts (compounds 1–7[OTf]), where [OTf]- stands for the trifluoromethanesulfonate anion, we performed comprehensive spectroscopic and dynamic studies on the photoinduced anion migration in toluene. Our aim is to probe if the anion migration is associated with an intrinsic barrier or is barrier free. After the occurrence of excited-state intramolecular charge transfer (ESICT) in 1–7, the charge redistribution of the cation triggers the translocation of the counter anion [OTf]–, resulting in emission spectral temporal evolution. As a result, we describe the photoinduced anion migration by introducing spectral response function C(t), a concept adopted from the solvent diffusional relaxation. The experimental results indicate that the anion migration lacks intrinsic barrier, i.e., the relaxation dynamics can be described by a biased Brownian motion along the charge transfer direction. The experimental findings are also qualitatively supported by theoretical calculations including restrained electrostatic potential (RESP) and hole-electron distribution analyses.
光诱导阴离子在供体-π-受体+(离子)-分子中转移的启示
通过战略性地设计和合成一系列新的鏻盐(化合物 1-7[OTf])(其中 [OTf]- 代表三氟甲磺酸阴离子),我们对甲苯中光诱导的阴离子迁移进行了全面的光谱和动态研究。我们的目的是探究阴离子迁移是与固有障碍相关还是无障碍。在 1-7 中发生激发态分子内电荷转移(ESICT)后,阳离子的电荷再分布引发了反阴离子 [OTf]- 的迁移,从而导致发射光谱的时间演变。因此,我们引入了光谱响应函数 C(t)来描述光诱导的阴离子迁移,这一概念源自溶剂扩散弛豫。实验结果表明,阴离子迁移缺乏本征障碍,即弛豫动力学可以用沿电荷转移方向的偏布朗运动来描述。包括约束静电位(RESP)和空穴-电子分布分析在内的理论计算也定性地支持了实验结果。
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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