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@ARTICLE{Veroutis:888670,
author = {Veroutis, Emmanouil and Merz, Steffen and Eichel,
Rüdiger-A. and Granwehr, Josef},
title = {{I}ntra- and inter-molecular interactions in choline-based
ionic liquids studied by 1{D} and 2{D} {NMR}},
journal = {Journal of molecular liquids},
volume = {322},
issn = {0167-7322},
address = {New York, NY [u.a.]},
publisher = {Elsevier},
reportid = {FZJ-2020-05105},
pages = {114934 -},
year = {2021},
abstract = {Choline acetate [Ch]$^+$[OAc]$^−$ and choline
trifluoroacetate [Ch]$^+$[TFA]$^−$ mixed with 30 wt\%
H$_2$O have been characterized by variable temperature 1D
and 2D 1H/19F NMR. It was found that the cation, anion and
water molecules participate in a strong local H-bond
network, but there was no evidence for the formation of
large clusters of ions. Weaker association effects were
observed for the trifluoroacetate than for the acetate,
originating from the higher anion acidity of TFA. Rotational
correlation times, which were extracted by temperature
dependent spin–lattice relaxation measurements, indicated
that cations, anions and H$_2$O exhibit collective
reorientation even at room temperature. At the same time, no
significant long-range correlations in the translational
motion of the ions could be observed from PFG diffusion
measurements. Moreover, 1D and 2D NOE experiments showed
that both ions share close proximity to water molecules for
a period on the order of 0.2 s at room temperature. It is
deduced that the ions exist in a solvent-shared ion pair
(SIP) configuration, with strongly correlated short-range
dynamics between the choline cation and the H$_2$O
molecules, indicating a similar behavior of these ILs to a
deep eutectic solvent with water as Lewis acid. A reason for
this observation, which is supported by a high entropy term
in the activation process particularly at low temperatures,
could be a fairly static configuration with water near the
–N(CH$_3$)$_3$ center of the choline, and relaxation
caused by pseudorotation due to reordering of the H-bond
network.},
cin = {IEK-9},
ddc = {540},
cid = {I:(DE-Juel1)IEK-9-20110218},
pnm = {131 - Electrochemical Storage (POF3-131) / 1223 - Batteries
in Application (POF4-122)},
pid = {G:(DE-HGF)POF3-131 / G:(DE-HGF)POF4-1223},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000610834000099},
doi = {10.1016/j.molliq.2020.114934},
url = {https://juser.fz-juelich.de/record/888670},
}