A Combined Experimental/Computational Study of Dicationic Ionic Liquids with Bromide and Tungstate Anions.

A panel of dicationic ionic liquids (DILs) with different rigid xylyl (ortho, meta, para) spacers and different anions (bromide and tungstate) has been synthetised and characterised through different experimental and computational techniques. Differences and analogies between the systems are analysed using information derived from their DFT structures, semiempirical dynamics, thermal behaviour, and catalytic properties versus the well-known reaction of CO2 added to epichlorohydrin. A comparison between the proposed systems and some analogues that present non-rigid spacers shows the key effect displayed by structure rigidity on their characteristics. The results show an interesting correlation between structure, flexibility, properties, and catalytic activity.

A Specific Interaction between Ionic Liquids' Cations and Reichardt's Dye.

Solvatochromic probes are often used to understand solvation environments at the molecular scale. In the case of ionic liquids constituted by an anion and a cation, which are designed and paired in order to obtain a low melting point and other desirable physicochemical properties, these two indivisible components can interact in a very different way with the probe. This is the case with one of the most common probes: Reichardt's Dye. In the cases where the positive charge of the cation is delocalized on an aromatic ring such as imidazolium, the antibonding orbitals of the positively charged aromatic system are very similar in nature and energy to the LUMO of Reichardt's Dye. This leads to an interesting, specific cation-probe interaction that can be used to elucidate the nature of the ionic liquids' cations. Parallel computational and experimental investigations have been conducted to elucidate the nature of this interaction with respect to the molecular structure of the cation.

Expanding the Chemical Space of Benzimidazole 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.

Synthesis and characterization of divalent metal-betaine-bistriflimide complexes: a property comparison with metal bistriflimide salts.

A panel of metal-betaine-bistriflimide complexes (with minimum formula M[Bet]2[Tf2N]2, where M = Mg, Ca, Zn, Cu and Ni) has been prepared in high purity and a quantitative yield. In parallel, a series of metal bistriflimide salts (sharing the same metal cations) has been synthesized and characterized though the same set of techniques. The current work presents a first comprehensive investigation of the physical-chemical properties of these two classes of metal systems, whose importance in a variety of applicative fields was not yet matched, to the best of our knowledge, by an adequate study of their characteristics. All the considered compounds have been spectroscopically, thermally and electrochemically characterized, and their solubility characteristics assessed, gaining insights into the role of metal cations in the definition of their properties. On the other hand, the evident effect of the betaine coordination on the prepared complexes' solubility, thermal stability, melting point, glass and solid-solid transitions, redox behaviour and electrochemical window was ascertained, providing results which would allow a more informed use and application of these classes of divalent metal complexes.

Betaine mediated enhancement of thermal stability and acidity tolerance of vanadium(V) solutions.

A panel of novel vanadium(IV)-betaine complexes has been synthesized according to new and efficient methodologies and characterized through both spectroscopic techniques and thermal analyses. Vanadium(IV)-betaine solutions have been electrochemically oxidized and the effect of betaine ligands on the thermal and pH stability of vanadium(V) solutions has been evaluated under different temperature and acidity conditions. The obtained results displayed a remarkable effect for both of the examined parameters, achieving the preparation of aqueous vanadium(V) solutions displaying long term stability at more than 55 °C under mild acidic conditions. The species formed in the betaine rich vanadium(V) solutions have been sprectroscopically identified in relationship with the acidity of the solution, and the obtained results were confirmed through computational techniques. Vanadium-betaine based solutions have been finally tested in a lab-scale redox flow battery setup, providing preliminary insight into the possible use of this type of electrolyte in VRFBs.

The Structure-Property Relationship of Pyrrolidinium and Piperidinium-Based Bromide Organic Materials.

Two couples of dicationic ionic liquids, featuring pyrrolidinium and piperidinium cations and different linker chains, were prepared and characterized. 1,1'-(propane-1,3-diyl)bis(1-methylpyrrolidinium) bromide, 1,1'-(octane-1,8-diyl)bis(1-methylpyrrolidinium) bromide, 1,1'-(propane-1,3-diyl)bis(1-methylpiperidinium) bromide, and 1,1'-(octane-1,8-diyl)bis(1-methylpiperidinium) bromide were synthesized in quantitative yields and high purity and thermally characterized through TGA and DSC analysis. In this study, we propose a preliminary comparative evaluation of the effect of the linker chain length and of the size of the aliphatic ammonium ring on the thermal and solubility properties of bromide dicationic ionic liquids.

An insight into the intermolecular vibrational modes of dicationic ionic liquids through far-infrared spectroscopy and DFT calculations.

Dicationic ionic liquids (DILs) are a subclass of the ionic liquid (IL) family and are characterized by two cationic head groups linked by means of a spacer. While DILs are increasingly attracting interest due to their peculiar physico-chemical properties, there is still a lack of understanding of their intermolecular interactions. Herein, we report our investigations on the intermolecular vibrational modes of two bromide DILs and of a bistriflimide DIL. The minimal possible neutral cluster of ions was studied as a simplified model of these systems and was optimized at the DFT level. Normal modes of two sandwich-like conformers were then calculated using the harmonic approximation with analytical computation of the second derivatives of molecular energy with respect to the atomic coordinates. The calculated spectra were compared to far-infrared experimental spectra and two groups of peaks over three, for the two bromide DILs, and three over five, for the Tf2N- DIL, were described by the proposed neutral cluster model. Therefore, this model represents a reliable and computationally affordable model for the exploration of the intermolecular interactions of this kind of system.

Systematic Synthesis and Properties Evaluation of Dicationic Ionic Liquids, and a Glance Into a Potential New Field.

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.