Abstract
Chiral molecular assemblies have attracted considerable attention because of their interesting physical properties, such as spin-selective electron transport. Cation-anion salts of three azolium cations, imidazolium (HIm(+)), triazolium (HTrz(+)), and thiazolium (HThz(+)), in combination with a chiral camphorsulfonate (1S-CS(-)) and their racemic compounds (rac-CS(-)) were prepared and compared in terms of phase transitions, crystal structures, dynamics of constituent molecules, dielectric responses, and proton conductivities. The cation-anion crystals containing HIm(+) showed no significant difference in proton conductivity between the homochiral and racemic crystals, whereas the HTrz(+)-containing crystals showed higher proton conductivity and lower activation energy in the homochiral form than in the racemic form. A two-dimensional hydrogen-bonding network consisting of HTrz(+) and -SO(3)(-) groups and similar in-plane rotational motion was observed in both crystals; however, the HTrz(+) cation in the homochiral crystal exhibited the rotational motion modulated with translational motion, whereas the HTrz(+) cation in the racemic crystal exhibited almost steady in-plane rotational motion. The different motional degrees of freedom were confirmed by crystal structure analyses and temperature- and frequency-dependent dielectric constants. In contrast, steady in-plane rotational motion with the thermally activated fluctuating motion of CS(-) was observed both in homochiral and racemic crystals containing HIm(+), which averaged the motional space of protons resulting in similar dielectric responses and proton conductivities. The control of motional degrees of freedom in homochiral crystals affects the proton conductivity and is useful for the design of molecular proton conductors.