Fluoride ion sensing with an acridinium borane
Fluoride ion sensing with an acridinium borane
复制标题
使用吖啶硼烷进行氟离子传感
DOI：
10.1139/cjc-2022-0080
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发表时间：
2022
影响因子：
1.1
通讯作者：
Gabbaï, F. P.
中科院分区：
文献类型：
--
作者：
Liu, W.-C.;Gabbaï, F. P.
随着我们对阳离子硼烷化学的持续兴趣，我们已经合成了1-dimesitylboron-4-(N-methyl-9-acridinium)-phenylene，的四氟硼酸盐，它作为一个开启的氟离子传感器，在与氟化物结合时明显地从黄色变成橙色。为了了解这种反应活性，我们用光谱分析和计算分析了阳离子和氟硼酸盐的加合物。紫外-可见光谱和含时密度泛函理论计算表明，变色的基础是分子内电荷转移带的低能红移。为进一步探索该体系，进行了电化学研究。循环伏安分析表明，氟离子结合后的第一个还原波中，阳离子发生可逆单电子还原，阴极位移约为−0.12V。阳离子的化学还原生成了吖啶硼烷自由基，电子顺磁共振光谱证实了这一点。
With our continuing interest in the chemistry of cationic boranes, we have synthesized the tetrafluoroborate salt of 1-dimesitylboron-4-(N-methyl-9-acridinium)-phenylene, which acts as a turn-on fluoride anion sensor, visibly changing from yellow to orange upon binding fluoride. To understand this reactivity, we spectroscopically and computationally analyzed the cation and fluoroborate adduct. Ultraviolet–visible spectroscopy and time-dependent density functional theory calculations revealed the basis of the color change to be a low energy redshift in a intramolecular charge transfer band. Electrochemical studies were undertaken to further probe this system. Cyclic voltammetry indicated a reversible one-electron reduction for the cation and a cathodic shift of −0.12 V in the first reduction wave upon fluoride binding. Chemical reduction of the cation yielded the acridine borane radical, which was verified by electron paramagnetic resonance spectroscopy.