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Nanocage formation and structural anomalies in imidazolium ionic liquid glasses governed by alkyl chains of cations. / Bakulina, Olga D.; Ivanov, Mikhail Yu; Prikhod'ko, Sergey A. et al.
In: Nanoscale, Vol. 12, No. 38, 14.10.2020, p. 19982-19991.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Nanocage formation and structural anomalies in imidazolium ionic liquid glasses governed by alkyl chains of cations
AU - Bakulina, Olga D.
AU - Ivanov, Mikhail Yu
AU - Prikhod'ko, Sergey A.
AU - Pylaeva, Svetlana
AU - Zaytseva, Irina V.
AU - Surovtsev, Nikolay V.
AU - Adonin, Nicolay Yu
AU - Fedin, Matvey V.
N1 - Russian Science Foundation № 19-13-00071.
PY - 2020/10/14
Y1 - 2020/10/14
N2 - Intriguing nanostructuring anomalies have been recently observed in imidazolium ionic liquids (ILs) near their glass transition points, where local density around a nanocaged solute progressively grows up with temperature. Herewith, we for the first time demonstrate experimentally and theoretically, that these anomalies are governed by alkyl chains of cations and crucially depend on their length. Electron Paramagnetic Resonance (EPR) spectroscopy on a series of ILs [Cnmim]BF4 (n = 0-12) shows that only the chains with n = 3-10 favor anomaly. Moreover, remarkable even vs. odd n peculiarities were systematically observed. Finally, similar anomaly was for the first time observed for a non-IL glass of dibutyl phthalate, which structurally mimics cations of imidazolium ILs. Therefore, such anomalous density behavior in a glassy state nanocage goes far beyond ILs and proves to be a more general phenomenon, which can be structurally tuned and rationally adjusted for various potential applications in nanoscale materials.
AB - Intriguing nanostructuring anomalies have been recently observed in imidazolium ionic liquids (ILs) near their glass transition points, where local density around a nanocaged solute progressively grows up with temperature. Herewith, we for the first time demonstrate experimentally and theoretically, that these anomalies are governed by alkyl chains of cations and crucially depend on their length. Electron Paramagnetic Resonance (EPR) spectroscopy on a series of ILs [Cnmim]BF4 (n = 0-12) shows that only the chains with n = 3-10 favor anomaly. Moreover, remarkable even vs. odd n peculiarities were systematically observed. Finally, similar anomaly was for the first time observed for a non-IL glass of dibutyl phthalate, which structurally mimics cations of imidazolium ILs. Therefore, such anomalous density behavior in a glassy state nanocage goes far beyond ILs and proves to be a more general phenomenon, which can be structurally tuned and rationally adjusted for various potential applications in nanoscale materials.
KW - NANOSTRUCTURAL ORGANIZATION
KW - SPIN PROBES
KW - DYNAMICS
KW - SOLVENTS
KW - LENGTH
KW - EPR
KW - HETEROGENEITIES
KW - VISCOSITY
KW - BEHAVIOR
KW - SALTS
UR - http://www.scopus.com/inward/record.url?scp=85092741243&partnerID=8YFLogxK
U2 - 10.1039/d0nr06065h
DO - 10.1039/d0nr06065h
M3 - Article
C2 - 32996529
AN - SCOPUS:85092741243
VL - 12
SP - 19982
EP - 19991
JO - Nanoscale
JF - Nanoscale
SN - 2040-3364
IS - 38
ER -
ID: 25616623