Alkylphosphonium carboxylate ionic liquids with tuned microscopic structures and properties

Abstract

Eleven pure alkylphosphonium carboxylate ionic liquids were synthesised following a reliable and accessible route. Tetrabutylphosphonium and tetradecyltrihexylphosphonium cations were associated to a variety of [R COO]– anions with R varying...

Improved Reversible and Selective SO2 Absorption by a Stable Phosphonium Carboxylate Ionic Liquid

“…Thus, σ has been scaled by a factor 0.95 in order to correct the systematic underestimation of densities while keeping the constancy and transferability of the model. 23 The distance between the centers of mass of the fragments, the geometric parameters, the atomic partial charges of molecules and ions, as well as the dipole moments of fragments were taken taken either from the CL&Pol force field 28 or from a previous study in which the missing parameters for the phosphonium carboxylate ILs under study were determined. 23 Only the distance between the centers of mass of CO 2 and SO 2 and the various fragments of [P 4,4,4,4 ][TetrazC 1 COO] have been calculated through a geometry optimization using dispersion-corrected density functional theory (DFT-D3) 34 at the B97-D3/cc-pVDZ level (Table S8).…”

“…This observation seems to contradict the expected deshielding effect of hydrogen bonds on protons but can be explained by the solvation of SO 2 around the O COO − site that decreases the interaction between the negatively charged headgroup of the anion and the H α of the cation. 23 The signals related to the anion are shifted downfield, indicating a decrease in electron density, likely due to the electrophilic nature of the sulfur atoms interacting with the carboxylate anion.…”

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

“…The stability of these aggregates was explained by the interactions of the counterions, located at the periphery of the cation clusters. More recently Scaglione et al [4] have also reported evidence of anion-anion interactions in one phosphonium tetrazolate IL with unique physical-chemical properties using molecular dynamics simulation and small angle X-ray scattering. In the case, it is the delocalization of the charge in the tetrazole ring of the anion that allows for an unexpected proximity of the anions in the liquid salt.Tetracyanoborate ions [B(CN)4] − are known to form ILs with low density and low viscosity, [5] with relatively high electrical conductivity [6] and capable of dissolving large quantities of CO2.…”

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

“…More recently Scaglione et al 4 have also reported evidence of anion−anion interactions in one phosphonium tetrazolate IL with unique physical−chemical properties using molecular dynamics (MD) simulation and small-angle X-ray scattering (SAXS). In this case, it is the delocalization of the charge in the tetrazole ring of the anion that allows for an unexpected proximity of the anions in the liquid salt.…”

“…More recently Scaglione et al . have also reported evidence of anion–anion interactions in one phosphonium tetrazolate IL with unique physical–chemical properties using molecular dynamics (MD) simulation and small-angle X-ray scattering (SAXS).…”