RESUMO
In this study, we systematically analyze the surface tension and Hansen solubility parameters (HSPs) of imidazolium-based ionic liquids (ILs) with different anions ([NTf2]-, [PF6]-, [I]-, and [Br]-). These anions are combined with the classical 1-alkyl-3-methyl-substituted imidazolium cations ([CnC1Im]+) and a group of oligoether-functionalized imidazolium cations ([(mPEGn)2Im]+) based on methylated polyethylene glycol (mPEGn). In detail, the influences of the length of the alkyl- and the mPEGn-chain, the anion size, and the water content are investigated experimentally. For [CnC1Im]+-based ILs, the surface tension decreases with increasing alkyl chain length in all cases, but the magnitude of this decrease depends on the size of the anion ([NTf2]- < [PF6]- < [Br]- ≤ [I]-). Molecular dynamics (MD) simulations on [CnC1Im]+-based ILs indicate that these differences are caused by the interplay of charged and uncharged domains, in particular in the different anions, which affects the ability of the alkyl chains of the cation to orient toward the liquid-gas interface. An increase in the mPEGn-chain length of the [(mPEGn)2Im][A] ILs does not significantly influence the surface tension. These changes upon variation of the cation/anion combination do not correlate with the evolution of the HSPs for the two sets of ILs. Finally, our data suggest that significant water contents up to water mole fractions of x(H2O) = 0.25 do not significantly affect the surface tension of the studied binary IL-water mixtures.
RESUMO
Separation and reuse of the catalytically active metal complexes are persistent issues in homogeneous catalysis. Supported Ionic Liquid Phase (SILP) catalysts, where the catalytic center is dissolved in a thin film of a stable ionic liquid, deposited on a solid support, present a promising alternative. However, the dissolution of the metal center in the film leaves little control over its position and its activity. We present here four novel, task-specific ionic liquids [FPhn ImH R]I (n=1, 2; R=PEG2 , C12 H25 ), designed to self-assemble on a silica surface without any covalent bonding and offering a metal binding site in a controlled distance to the support. Advanced multinuclear solid-state NMR spectroscopic techniques under Magic Angle Spinning, complemented by molecular dynamics (MD) simulations, allow us to determine their molecular conformation when deposited inside SBA-15 as a model silica support. We provide here conceptual proof for a rational design of ionic liquids self-assembling into thin films, opening an avenue for a second, improved generation of SILP catalysts.
