Interionic interactions in imidazolic ionic liquids probed by soft X-ray absorption spectroscopy.
This work investigates pure ionic liquids (ILs) derived from an imidazolium ring with different carbonic chains and halides or bis(trifluoromethanesulfonilimide) (TFSI(-)) as anions, using X-ray absorption near edge spectroscopy (XANES) at different energies (N, S, O, F, and Cl edges) to probe the interionic interactions. XANES data show that the interaction with the anion is weaker when the cation is an imidazolium than when the salt is formed by smaller cations, as lithium, independently of the length of the carbonic chain attached to the imidazolium cation. The results also show that, for all studied ILs, it is not observed any influence of the anion on the XANES spectra of the cation, nor the opposite. 1-Methylimidazolium with Cl(-), a small and strongly coordinating anion, presents in the N K XANES spectrum a splitting of the band corresponding to nitrogen in the imidazolic ring, indicating two different chemical environments. For this cation with TFSI(-), on the contrary, this splitting was not observed, showing that the anion has a weaker interaction with the imidazolic ring, even without a lateral carbonic chain.
Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, CP 26.077, CEP 05513-970, São Paulo, SP, Brazil. farod@iq.usp.br
Fabio
F
Rodrigues
Douglas
D
Galante
Gustavo M
GM
do Nascimento
Paulo S
PS
Santos