Side chain length-dependent dynamics and conductivity in self-assembled ion channels

Journal
The journal of physical chemistry C  
Volume
126
Issue
27
Start Page
10995
End Page
1006
Citation
Journal of Physical Chemistry C 127 (26): 10995-11006 (2022)
Publisher DOI
10.1021/acs.jpcc.2c03023
Scopus ID
2-s2.0-85134847182
Publisher
Soc.
We study the molecular mobility and electrical conductivity of a homologous series of linear shaped columnar ionic liquid crystals ILCn, (n = 8, 10, 12, 14, 16) using broadband dielectric spectroscopy (BDS), specific heat spectroscopy (SHS), and X-ray scattering. We aim to understand how the alkyl chain length influences the dynamics and electric conductivity in this system. Two dielectrically active relaxation modes are observed, the γand the αcore process, that correspond to the localized fluctuations of the alkyl chains and cooperative motions of the aromatic core in the columns, respectively. Both the γrelaxation and the αcore process slow down with increasing alkyl chain length. SHS reveals one relaxation process, the αalkyl process that has a similar temperature dependence as that of the αcore process for ILC12, 14, and 16 but shifts to higher temperature for ILC8 and 10. For ILC12, 14, and 16, the absolute values of DC conductivity increase by 4 orders of magnitude at the transition from the plastic crystalline to hexagonal columnar phase. For ILC8 and 10, the DC conductivity behavior is similar to ionic liquids, where the conductivity is coupled with structural relaxation. Small-angle X-ray investigations reveal that both the intercolumnar distance and the disorder coherence length increase with alkyl chain length; conversely, the DC conductivity decreases monotonically.
DDC Class
530: Physik
600: Technik