Dicationic ionic liquids (DILs), a subset of the ionic liquid (IL) family, have attracted growing interest in recent years, and the range of applications within which they are investigated is constantly expanding. However, data which allows structure to property correlation of a DIL is still limited, and thus selecting an appropriate salt to address a specific challenge can be problematic. In comparison to traditional ILs, DILs physico-chemical properties can be tuned by changing the length and type of spacer which connects the cationic heads as well as the type of cation. This in turn could give rise to symmetrical or asymmetrical DILs. In this work, a systematic study of a homogeneous class of 12 dibromide DILs and 12 di-carboxylate salts has been performed. The latter class of DILs were also compared to mono cation derivatives. The different traditional exchange methods to prepare carboxylate DILs have been evaluated and an insight into the drawbacks encountered is also presented. Prepared DILs were characterized (NMR, TGA, DSC) allowing the influence of the structure on their thermal stability to be understood. Most DILs were obtained as solid salts after careful drying. For some of these compounds, a new possible application was studied, namely their use as hydrogen bond acceptors (HBA) of deep eutectic mixtures, showing again some significant structural related effects.
The minimal cluster of ions represents a reliable and computationally affordable model for the exploration of the intermolecular interactions of dicationic ionic liquids.
Benzimidazole dicationic ionic liquids (BDILs) have not yet been widely explored in spite of their potential. Therefore, two structurally related families of BDILs, paired with either bromide or bistriflimide anions and bearing alkyl spacers ranging from C3 to C6, have been prepared. Their thermal properties have been studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), while their electrical properties have been assessed by cyclic voltammetry (CV). TG analysis confirmed the higher stability of the bistriflimide BDILs over the bromide BDILs, with minor variation within the two families. Conversely, DSC and CV allowed for ascertaining the role played by the spacer length. In particular, the thermal behavior changed dramatically among the members of the bistriflimide family, and all three possible thermal behavior types of ILs were observed. Furthermore, cyclic voltammetry showed different electrochemical window (C3(C1BenzIm)2/2Tf2N < C4(C1BenzIm)2/2Tf2N, C5(C1BenzIm)2/2Tf2N < C6(C1BenzIm)2/2Tf2N) as well as a reduction peak potential, shape, and intensity as a function of the spacer length. The results obtained highlight the benefit of accessing a more structurally diverse pool of compounds offered by dicationic ILs when compared to the parent monocationic ILs. In particular, gains are to be found in the ease of fine-tuning their properties, which translates in facilitating further investigations toward BDILs as designer solvents and catalysts.
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