Expanding the Chemical Space of Benzimidazole Dicationic Ionic Liquids

• Main Authors: Andrea Mezzetta, Luca Guglielmero, Angelica Mero, Giorgio Tofani, Felicia D’Andrea, Christian Silvio Pomelli, Lorenzo Guazzelli
• Format: Article
• Language: English
• Published: MDPI AG 2021-07-01
• Series: Molecules
• Subjects: ionic liquids; green solvents; benzimidazole; dicationic ionic liquids; thermal stability; thermal behavior
• Online Access: https://www.mdpi.com/1420-3049/26/14/4211

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.