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首页> 外文期刊>Chemistry: A European journal >Synthesis of room-temperature ionic liquids with the weakly coordinating [Al(OR~F)_4]~- Anion (R~F=C(H)(CF _3)_2) and the determination of their principal physical properties
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Synthesis of room-temperature ionic liquids with the weakly coordinating [Al(OR~F)_4]~- Anion (R~F=C(H)(CF _3)_2) and the determination of their principal physical properties

机译：弱配位[Al（OR〜F）_4]〜-阴离子（R〜F = C（H）（CF _3）_2）的室温离子液体的合成及其主要物理性质的测定

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A large series of ionic liquids (ILs) based on the weakly coordinating alkoxyaluminate [Al(hfip)_4]~- (hfip: hexafluoroisopropoxy) with classical as well as functionalized cations were prepared, and their principal physical properties determined. Melting points are between 0 ([C _4MMIM][Al(hfip)_4]) and 69 °C ([C_3MPip] [Al(hfip)_4]); three qualify as room-temperature ILs (RTILs). Crystal structures for six ILs were determined; their structural parameters and anion-cation contacts are compared here with known ILs, with a special focus on their influence on physical properties. Moreover, the biodegradability of the compounds was investigated by using the closed-bottle and the manometric respirometry test. Temperature-dependent viscosities and conductivities were measured between 0 and 80 °C, and described by either the Vogel-Fulcher-Tammann (VFT) or the Arrhenius equations. Moreover, conductivities and viscosities were investigated in the context of the molecular volume, V_m. Physical property-V_m correlations were carried out for various temperatures, and the temperature dependence of the molecular volume was analyzed by using crystal structure data and DFT calculations. The IL ionicity was investigated by Walden plots; according to this analysis, [Al(hfip)_4]~- ILs may be classified as "very good to good ILs" while [C_2MIM][Al(hfip)_4] is a better IL than [C_2MIM][NTf_2]. The dielectric constants of ten [Al(hfip)_4]~- ILs were determined, and are unexpectedly high (ε_r=11.5 to 16.8). This could be rationalized by considering additional calculated dipole moments of the structures frozen in the solid state by DFT. The determination of hydrogen gas solubility in [Al(hfip)_4]~- RTILs by high-pressure NMR spectroscopy revealed very high hydrogen solubilities at 25 °C and 1 atm. These results indicate the significant potential of this class of ILs in manifold applications. New RTILs: A series of ionic liquids (ILs) based on the weakly coordinating anion [Al(hfip)_4]~- (see figure) has been synthesized and thoroughly characterized. The ILs were found to have widely interesting properties that suggest potential for these ILs in many applications (hfip=hexafluoroisopropoxy).
机译：制备了一系列基于弱配位的烷氧基铝酸盐[Al（hfip）_4]〜-（hfip：六氟异丙氧基）的离子液体，并确定了其主要物理性质。熔点在0（[C _4MMIM] [Al（hfip）_4]）和69°C（[C_3MPip] [Al（hfip）_4]）之间;三个符合室温IL（RTIL）。确定了六个IL的晶体结构。在此将它们的结构参数和阴离子-阳离子接触与已知的离子液体进行比较，并特别关注它们对物理性能的影响。此外，通过使用密闭瓶法和测压呼吸法试验研究了化合物的生物降解性。温度相关的粘度和电导率在0至80°C之间测量，并通过Vogel-Fulcher-Tammann（VFT）或Arrhenius方程进行描述。此外，在分子体积V_m的背景下研究了电导率和粘度。在各种温度下进行物理性质-V_m相关性，并通过使用晶体结构数据和DFT计算来分析分子体积的温度依赖性。用Walden图研究了IL离子性。根据该分析，可以将[Al（hfip）_4]〜-IL归类为“非常好对IL”，而[C_2MIM] [Al（hfip）_4]比[C_2MIM] [NTf_2]更好。确定了十个[Al（hfip）_4]〜-IL的介电常数，并且其介电常数出乎意料地高（ε_r= 11.5至16.8）。这可以通过考虑通过DFT固态冻结的结构的其他计算偶极矩来合理化。高压NMR光谱法测定[Al（hfip）_4]-RTIL中的氢气溶解度，显示在25°C和1 atm的氢气溶解度非常高。这些结果表明这类IL在多用途应用中具有巨大的潜力。新的RTIL：已合成并充分表征了一系列基于弱配位阴离子[Al（hfip）_4]〜-的离子液体（IL）。发现IL具有广泛有趣的性质，表明在许多应用中这些IL具有潜力（hfip ＝六氟异丙氧基）。

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