The molecular structures and the relationships between the calculated molecular and observed bulk phase properties of phosphonium-based ionic liquids

The chemical stability of phosphonium-based ionic liquids under gamma irradiation

“…The presence of only one UVabsorption band at a wavelength longer than 250 nm is consistent with the DFT calculation for this IL reported in literature. 17 That calculation predicts that there are a smaller number of allowed electronic transitions in this wavelength range for [P 14666 ][NTf 2 ] compared to [P 14666 ][Br]. 17 As observed for [P 14666 ][Br], the intensity of the 290 nm absorption band increased with irradiation time.…”

“…17 That calculation predicts that there are a smaller number of allowed electronic transitions in this wavelength range for [P 14666 ][NTf 2 ] compared to [P 14666 ][Br]. 17 As observed for [P 14666 ][Br], the intensity of the 290 nm absorption band increased with irradiation time. Although we see the radiolytic decomposition products, CHF 3 and C 2 F 6 , from the anion moiety [NTf 2 ] in the headspace, these molecules do not absorb light at wavelengths >250 nm and hence we did not see any UV absorption corresponding to these species.…”

Corrosion of carbon steel in the [P 14666 ][Br] ionic liquid: The effects of γ-radiation and cover gas

“…However, an addition of organic compounds to the IL can change its viscosity and ion mobility. The ionic liquid can be considered as network of ion-pairs that is loosely held by the electrostatic forces between cations and anions and dispersion forces between the alkyl chains of the cations [41]. The addition of a substantial amount of hexane weakens the intermolecular dispersion interaction between IL molecules and will result in a decrease in its viscosity.…”

“…We have reported on DFT (density functional theory) calculations and molecular dynamic simulations to determine the molecular structures and the macroscopic properties (such as viscosity and conductivity) of various phosphonium ILs [41]. These studies have shown that the Br  in the IL does not move freely and is not an effective charge carrier.…”

Phosphonium salts and P-ylides

“…The molecular and electronic structures of six PILs, all bearing the [P 66614 ] cation, were obtained via DFT quantum chemical calculations by Clara Wren and co-workers. 144 A strong correlations between the calculated and the measured physical and chemical properties was observed. Yonekura and Grinstaff prepared a series of mono-and di-cationic phosphonium cations and combined them with seven monoanionic counterions.…”