Unravelling free volume in branched-cation ionic liquids based on silicon

Abstract

We have explored the branching of ionic liquid cation sidechains utilizing silicon as the backbone and found this structural feature to lead to fluids of remarkably low density and viscosity....

A kinetics study of copper-catalysed click reactions in ionic liquids

“…As in other [NTf 2 ] − ILs, an induction period could be observed in the kinetic profile in the branched cation IL. While cation sidechain branching increases the free volume within the liquid, 23 and reduces the extent of IL nano-segregation, the similar result observed compared to [C 8 C 1 im][NTf 2 ] implies neither of these factors strongly influence these reaction outcomes.…”

“…Following the insight into the specific behavior of CuAAC catalysts in ILs obtained using liquid reagents, we wanted to understand if the explored systems would be suitable for CuAAC reactions involving an unsubstituted alkyne – gaseous acetylene. According to our previous work, 23 silicon branched ILs enhance the free volume within the liquid. This entropically contributes to gas absorption processes 23 and might have implications for applications such as IL-assisted synthesis involving gaseous reagents.…”

“…According to our previous work, 23 silicon branched ILs enhance the free volume within the liquid. This entropically contributes to gas absorption processes 23 and might have implications for applications such as IL-assisted synthesis involving gaseous reagents.…”

“…Functionalization of IL cations can lead to secondary interactions with metal centres as well as affecting the nanostructure of ILs. 22 These structural changes can also affect the free volume within the liquid, 23 which can be of importance for reactions involving gaseous reactants. A set of various imidazolium cation N -substituents including linear, branched, and hetero-atom functionalized sidechains have been incorporated to investigate their effect on the CuAAC reaction (Fig.…”

Attraction between Like Charged Ions in Ionic Liquids: Unveiling the Enigma of Tetracyanoborate Anions

“…8,9 These properties have encouraged us to include this bulky anion in our recent study of free volume enhancement in silicon-functionalized imidazolium-based ILs. 10 Introducing alkylsilane groups to a cation weakens cation−anion attraction, resulting in a higher fluidity and molar volume expansion 11,12 and, thus, greater void fraction, which become available for gas solute molecules.…”