Understanding and predicting the physical properties of ILs: (Monte Carlo augmented) Born-Fajans-Haber-Cycle approaches, a systematic temperature dependent experimental and theoretical investigation of the molecular and free volumes of solid and liquid IL

离子液体(ILS)由于具有广泛的应用前景，目前正受到人们的广泛关注。然而，随着这些材料的应用数量的增加，我们仍然对它们的基本性质的起源知之甚少。此外，目前很少有定量方法来预测未知盐类的性质。在针对特定应用设计新的ILS时，必须使用试错法，这限制了这一领域的进展。因此，能够在一个简单的程序中预测未知ILS的性质，将使ILS能够完成其作为设计者材料的命运，这种材料可以根据特定的应用而定制。在此背景下，我们最近发展了一个简单的，定量的解释ILS的相对较低的熔化温度(MP S)。该模型可以用简单的计算和最少的实验数据来预测离子液体的熔点、S和介电常数，具有很好的精度。因此，这项技术有可能被普通化学家用来帮助设计新的ILS。在这项建议中，我们描述了如何改进该模型以提高其预测的准确性以及解决该方法的问题案例，例如通过确定ILS的热力学性质以及室温离子液体的固态结构。初步结果表明，IL的(热化学)分子体积与盐的粘度和电导率之间存在简单的关系。在拟议的项目中，我们将在实验和理论基础上扩展这些关联。在对弱配位阴离子的研究中，我们发现氟化的烷氧基铝酸盐阴离子[Al(ORF)4]-的Li+盐在相对较低的温度下熔化。其中一种盐的熔点为42-45°C，这已经将这种材料归类为IL。以Li+为阳离子的离子液体(Li+-离子液体)目前非常少见，但作为电池和超级电容器的电解液以及有机化学中的Li+离子催化剂具有潜在的应用前景。在拟议的项目中，我们将开发氟化烷氧基铝酸盐阴离子的Li+盐的化学，并通过改变阴离子的结构和官能度来开发在常温下为液体的材料。此外，我们将研究阴离子的结构特征，这些结构特征导致了特定应用中Li+的高迁移率和可用性。我们将能够使用在项目期间开发的理论方法来帮助设计锂离子液体，并在必要时开发专门针对这种特殊类型的离子液体的新模型。

Ionic liquids (ILs) are currently receiving a great deal of attention due to their potential use in a wide range of applications. However, as the number of applications for these materials grows, we still know very little about the origins of their fundamental properties. Furthermore, there are currently very few quantitative methods to predict the properties of unknown salts. Trial and error methods must be used to design new ILs for particular applications, which limit the progress in this field. Thus, the ability to predict the properties of yet unknown ILs in a simple procedure, would allow ILs to fulfil their destiny as designer materials, which can be tailored to a specific application. In this context we have recently developed a simple, quantitative explanation of the relatively low melting temperatures of ILs (mp s). This model can be used to predict the mp s and dielectric constants of ILs with good accuracy using simple calculations and a minimum of experimental data. As such, this technique has the potential to be used by general chemists to help in the design of new ILs. In this proposal we describe how this model can be refined to improve the accuracy of its predictions as well as to solve problem cases for the method, e.g. by determining thermodynamic properties of ILs as well as solid-state structures of ambient temperature ionic liquids. Preliminary results suggest a simple relationship between the (thermochemical) molecular volume of an IL and the viscosity and conductivity of the salt. In the proposed project we will extend these correlations, both, on an experimental as well as theoretical basis. During our work on weakly coordinating anions we have discovered that the Li+ salts of fluorinated alkoxyaluminate anions [A1(ORF)4]- melt at relatively low temperatures. One of these salts has a melting point of 42-45 °C, which already classifies this material as an IL. ILs with Li+ as the cation (Li+-ionic liquids) are currently extremely rare, but have the potential for use as electrolytes in batteries and super capacitors and as Li+-ion catalysts for organic chemistry. During the proposed project we will develop the chemistry of Li+ salts of fluorinated alkoxyaluminate anions, and by changing the structure and functionality of the anion develop materials that are liquid at ambient temperatures. Moreover, we will investigate the structural features of the anion that lead to high Li+ mobility and availability for particular applications. We will be able to use the theoretical methods developed during the project to help in the design of Li+-ionic liquids and where necessary develop new models that are specific to this special type of IL.