Investigations of the Degenerate Intramolecular Charge Exchange in Symmetric Organic Mixed Valence Compounds: Solvent Dynamics of Bis(triarylamine)paracyclophane Redox Systems
Investigations of the Degenerate Intramolecular Charge Exchange in Symmetric Organic Mixed Valence Compounds: Solvent Dynamics of Bis(triarylamine)paracyclophane Redox Systems
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DOI：
10.1021/acs.jpcc.5b01386
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发表时间：
2015-04-23
影响因子：
3.7
通讯作者：
Grampp, Guenter
中科院分区：
文献类型：
--
作者：
Mladenova, Boryana;Kattnig, Daniel R.;Grampp, Guenter
三芳胺是光电子器件中重要的空穴传输组分。了解控制其分子内和分子间电子转移性质的因素对于有机空穴导体的应用和优化至关重要。在这里，我们报告的几个纯有机混合价化合物的基础上的双（三芳胺）paracyclophane结构单元，这是典型的分子导线的简并分子内电子交换反应。不同的桥接部分进行了比较，并证明了最重要的影响的溶剂环境上的电子转移速率。比较发现许多不同的溶剂的速率常数，我们发现，令人惊讶的是，电子转移反应是有限的溶剂动力学效应，并没有强烈的影响的特点的桥接部分，这是没有预料到的发现，这种类型的远程，热激活的分子内电荷转移从以前的研究。速率常数测定动态电子顺磁共振光谱。我们的洞察力是可能的，使用各种溶剂跨越了广泛的纵向弛豫时间（0.24 ps
Triarylamines are important hole-transport components in optoelectronic devices. Understanding the factors controlling their intra- and intermolecular electron transfer properties is crucial to the application and optimization of organic hole conductors. Here, we report on the degenerate intramolecular electron exchange reactions of several purely organic mixed valence compounds based on the bis(triarylamine)paracyclophane structural unit, which are archetypical molecular wires. Different bridging moieties are compared, and the foremost impact of the solvent environment on the rate of electron transfer is demonstrated. Comparing the rate constants found for many different solvents, we find that surprisingly the electron transfer reaction is limited by the solvent dynamic effect and not strongly impacted by the peculiarities of the bridging moiety, a finding which was not anticipated for this type of long-range, thermally activated intramolecular charge transfer from previous studies. Rate constants are measured by dynamic electron paramagnetic resonance spectroscopy. Our insight was possible using various solvents spanning a wide range of longitudinal relaxation times (0.24 ps