Torriero Angel A J, Siriwardana Amal I, Bond Alan M, Burgar Iko M, Dunlop Noel F, Deacon Glen B, MacFarlane Douglas R
School of Chemistry and ARC Special Research Centre for Green Chemistry, Monash University, Clayton, Victoria 3800, Australia.
J Phys Chem B. 2009 Aug 13;113(32):11222-31. doi: 10.1021/jp9046769.
The preparation and characterization of a series of ionic liquids based on S-alkyl thiolonium, S-alkyl thiotetrazolium, or S-alkyl thiobenzolium cations coupled with bis(trifluoromethanesulfonyl)amide, trifluoromethanesulfonate, alkyl phosphate, chloride, and hexafluorophosphate anions are reported. All are liquid at room temperature, except the chloride salt, which has a melting point of 92 degrees C. The electrochemical characteristics of this class of ionic liquid have been determined by cyclic voltammetry. Potential windows of the ionic liquids have been obtained at glassy carbon, platinum, and gold electrodes and found to be the largest at glassy carbon, but are limited by oxidation of the thioether-functionalized cation. The voltammetry of IUPAC reference potential scale systems, ferrocene/ferrocenium, cobaltocenium/cobaltocene, and decamethylferrocene/decamethylferrocenium have been evaluated, with the last being most widely applicable. Nonadditivity of Faradaic current is found in the voltammograms of decamethylferrocene in the presence of ferrocene and cobaltocenium. Diffusion coefficient, viscosity, ionic conductivity, double layer capacitance, and other physical properties have also been measured. The dependence of the diffusion coefficient vs viscosity follows the Stokes-Einstein relationship. The properties of the ionic liquids are compared with the related imidazolium family of ionic liquids.
报道了一系列基于S-烷基硫鎓、S-烷基硫代四唑鎓或S-烷基硫代苯鎓阳离子与双（三氟甲磺酰）酰胺、三氟甲磺酸盐、烷基磷酸盐、氯化物和六氟磷酸盐阴离子的离子液体的制备和表征。除了熔点为92℃的氯化物盐外，所有离子液体在室温下均为液体。通过循环伏安法测定了这类离子液体的电化学特性。在玻碳、铂和金电极上获得了离子液体的电位窗口，发现其在玻碳电极上最大，但受硫醚官能化阳离子氧化的限制。对IUPAC参考电位标度体系、二茂铁/二茂铁鎓、钴茂鎓/钴茂和十甲基二茂铁/十甲基二茂铁鎓的伏安法进行了评估，其中最后一种应用最广泛。在二茂铁和钴茂鎓存在下，十甲基二茂铁的伏安图中发现了法拉第电流的非加和性。还测量了扩散系数、粘度、离子电导率、双层电容和其他物理性质。扩散系数与粘度的关系遵循斯托克斯-爱因斯坦关系。将这些离子液体的性质与相关的咪唑鎓类离子液体进行了比较。
