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首页> 外文期刊>Spectrochimica acta, Part A. Molecular and biomolecular spectroscopy >ESR-spectroscopy in ionic liquids: Dynamic linebroadening effects caused by electron-self exchange reactions within the methylviologene redox couple
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ESR-spectroscopy in ionic liquids: Dynamic linebroadening effects caused by electron-self exchange reactions within the methylviologene redox couple

机译:离子液体中的ESR光谱:由甲基紫胶氧化还原对内的电子自交换反应引起的动态扩线效应

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摘要

Well-resolved ESR-spectra of the methylviologene radical cation (MV center dot+) are recorded in room-temperature liquid ions as solvents. The temperature dependences of the ESR-coupling constants are similar to those measured in classical organic solvents. Electron-self exchange rates are reported for the methylviologene redox couple (MV++/MV center dot+) in 1-butyl-3-methylimidazolium hexafluorophosphate (bmim(+)PF(6)(-)), 1-butlyl-3-methylimidazolium fluoroborate (bmim(+)BF(4)(-)) and 1-ethyl-3-imidazolium ethylsulfate (emim(+)O(3)SOEt(-)) within a temperature range of 350K <= T <= 460K. The diffusion controlled rate constants observed vary between 8.2 x 10(7) M-1 s(-1) and 1.2 x 10(9) M-1 s(-1). From temperature-dependent measurements the activation energies obtained range from 27.4 kJ/mol in emim(+)O(3)SOEt(-) to 42.1 kJ/mol in bmim(+)PF(6)(-), respectively. (c) 2005 Elsevier B.V. All rights reserved.
机译:在室温液态离子中作为溶剂记录了甲基紫罗兰自由基阳离子(MV中心点+)的良好分辨的ESR光谱。 ESR耦合常数的温度依赖性类似于在传统有机溶剂中测得的温度依赖性。报道了1-丁基-3-甲基咪唑六氟磷酸盐(bmim(+)PF(6)(-)),1-丁基-3-甲基咪唑氟硼酸酯中甲基紫罗兰烯氧化还原对(MV ++ / MV中心点+)的电子自交换率(bmim(+)BF(4)(-))和1-乙基-3-咪唑鎓乙基硫酸盐(emim(+)O(3)SOEt(-))在350K <= T <= 460K的温度范围内。观察到的扩散控制速率常数在8.2 x 10(7)M-1 s(-1)和1.2 x 10(9)M-1 s(-1)之间变化。从与温度有关的测量中,获得的活化能分别从emim(+)O(3)SOEt(-)中的27.4 kJ / mol到bmim(+)PF(6)(-)中的42.1 kJ / mol。 (c)2005 Elsevier B.V.保留所有权利。

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