1H and 13C NMR spectroscopy is employed to investigate the interaction of water with two imidazolium-based ionic liquids (ILs), 1-hexyl-3-methylimidazolium bromide ([C6mim]Br) and 1-octyl-3-methylimidazolium bromide ([C8mim]Br), at IL concentrations well above the critical aggregation concentration (CAC). The results are compared with those of the neat samples. To this aim, a detailed analysis of the changes in the 1H chemical shifts, 13C relaxation parameters, and 2D ROESY data due to the presence of water is performed. The results for both neat ILs are consistent with a packed structure where head-to-head, head-to-tail, and tail-to-tail contacts occur and where the site of maximal mobility restriction is at the polar head. At the lowest investigated water content, the presence of water influences mainly the environment around the IL polar head, slowing down the motional dynamics of the aromatic ring with respect to the alkyl chain. At higher water contents this difference diminishes, the motional freedom of the whole molecule increasing. The presence of ROESY cross-peaks between protons in the polar and apolar IL regions, as well as between protons in non-neighboring alkyl groups, at all investigated water contents suggests that the alkyl tails are not fully segregated in hydrophobic domains, as expected for micelle-like structures.

Cesare Marincola, F., Piras, C., Russina, O., Gontrani, L., Saba, G., Lai, A. (2012). NMR investigation of imidazolium-based ionic liquids and their aqueous mixtures. CHEMPHYSCHEM, 13(5), 1339-1346 [10.1002/cphc.201100810].

NMR investigation of imidazolium-based ionic liquids and their aqueous mixtures

Gontrani, L.
Membro del Collaboration Group
;
2012-01-01

Abstract

1H and 13C NMR spectroscopy is employed to investigate the interaction of water with two imidazolium-based ionic liquids (ILs), 1-hexyl-3-methylimidazolium bromide ([C6mim]Br) and 1-octyl-3-methylimidazolium bromide ([C8mim]Br), at IL concentrations well above the critical aggregation concentration (CAC). The results are compared with those of the neat samples. To this aim, a detailed analysis of the changes in the 1H chemical shifts, 13C relaxation parameters, and 2D ROESY data due to the presence of water is performed. The results for both neat ILs are consistent with a packed structure where head-to-head, head-to-tail, and tail-to-tail contacts occur and where the site of maximal mobility restriction is at the polar head. At the lowest investigated water content, the presence of water influences mainly the environment around the IL polar head, slowing down the motional dynamics of the aromatic ring with respect to the alkyl chain. At higher water contents this difference diminishes, the motional freedom of the whole molecule increasing. The presence of ROESY cross-peaks between protons in the polar and apolar IL regions, as well as between protons in non-neighboring alkyl groups, at all investigated water contents suggests that the alkyl tails are not fully segregated in hydrophobic domains, as expected for micelle-like structures.
2012
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/02 - CHIMICA FISICA
English
aggregation; ionic liquids; NMR spectroscopy; ROESY; water
Cesare Marincola, F., Piras, C., Russina, O., Gontrani, L., Saba, G., Lai, A. (2012). NMR investigation of imidazolium-based ionic liquids and their aqueous mixtures. CHEMPHYSCHEM, 13(5), 1339-1346 [10.1002/cphc.201100810].
Cesare Marincola, F; Piras, C; Russina, O; Gontrani, L; Saba, G; Lai, A
Articolo su rivista
File in questo prodotto:
File Dimensione Formato  
appo.pdf

solo utenti autorizzati

Tipologia: Versione Editoriale (PDF)
Licenza: Copyright dell'editore
Dimensione 576.53 kB
Formato Adobe PDF
576.53 kB Adobe PDF   Visualizza/Apri   Richiedi una copia

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/294524
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 42
  • ???jsp.display-item.citation.isi??? 41
social impact