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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion
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Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion

机译：吡咯烷烃离子液体吡咯烷烃的脉冲放射性和计算研究：二聚体自由基阴离子的检测

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摘要

A pulse radiolysis study on pyrrolidinium cation based ionic liquids is presented herein. Time-resolved absorption spectra for 1-methyl-1-propylpyrrolidinium dicyanamide (DCA) at 500 ns after the electron pulse show broad absorption bands at wavelengths below 440 nm and at 640 nm. In pyrrolidinium bis(trifluoromethylsulfonyl)imide (NTf_(2)) and tris(perfluoroethyl)trifluorophosphate (FAP) ILs, the transient absorption below 440 nm is much weaker. The absorption at 500 ns, which increases with wavelength from 500 nm to beyond 800 nm, was assigned to the tail of the solvated electron NIR absorption spectrum, since it disappears in the presence of N_(2)O. In the DCA IL, the presence of a reducing species was confirmed by the formation of pyrene radical anion. The difference in the transient species in the case of the DCA IL compared to other two ILs should be due to the anion, with cations being similar. In pseudohalide ILs such as DCA, radicals are formed by direct hole trapping by the anion (X~(–) + h~(+) → X~(?)), followed by addition to the parent anion. Prediction of the UV/vis absorption spectra of the dimer radical anion by computational calculation supports the experimental results. The oxidizing efficiency of (DCA)_(2)~(?–) and its reduction potential (E _((DCA)_(2)~(?–)/(2DCA~(–)))) have been determined.
机译：本文介绍了吡咯烷基阳离子阳离子离子液体的脉冲放射性研究。在电子脉冲显示在440nm以下的波长和640nm的波长下，在500ns下，在500ns处的1-甲基-1-丙基吡咯烷鎓二氰胺（DCA）的时间分辨吸收光谱。在吡咯烷酮双（三氟甲基磺酰基）酰亚胺（NTF_（2））和三（全氟乙基）三氟磷酸酯（FAP）ILS中，低于440nm的瞬态吸收是较弱的。 500ns的吸收，其波长从500nm到超过800nm增加，被分配给溶剂化的电子网鲁吸收光谱的尾部，因为它在N_（2）o存在下消失。在DCA IL中，通过形成芘基团的形成确认还原物种的存在。与其他两个ILS相比，DCA IL的瞬态物种的差异应该是由于阴离子，阳离子是相似的。在诸如DCA的假织物IL中，通过直接通过阴离子捕获（X〜（ - ）+ H〜（+）→X〜（α））来形成自由基，然后加入父阴离子。通过计算计算预测二聚体自由基阴离子的UV / Vis吸收光谱支持实验结果。 （DCA）_（2）〜（2）〜（α - ）的氧化效率及其还原电位（ e_（（DCA）_（2）〜（α - ）/（2dca〜（）））））已经确定了。

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