Temperature-Tuned Variable Confined Space for Modulating Dipolar Polarization of a Disc-Shaped Ammonium Ion

Free accessible confined space and loose interaction are crucial for most solid-state ionic motions. Here, by using a near-spherical anion and a disc-shaped ammonium as two distinct but rigid building blocks, we report a new ionic crystal, (HMIm)(3)[La(NO3)(6)] (HMIm = 1-methyl-1H-imidazol-3-ium), in which the different confined spaces of three (HMIm)(+) ions are fine-tuned over a broad temperature range. This effect can be utilized to modulate the dipolar polarization across a wide temperature/frequency range. Additionally, small-scale substitution of (HMIm)(+) by its isomer of almost identical shape/size affords molecular solid solutions, which can further tune the dipolar polarization by varying the doping ratio. It is revealed that the differences in dipole moment and hydrogen bond rather than that of shape/size lead to a distorted crystalline environment for these solid solutions. Overall, we provide an exceptional model for understanding and regulating the dipole motion of polar aromatic molecules/ions in a crystalline environment.

Automated summary

Free accessible confined space and loose interaction can be achieved in an ionic crystal (HMIm)(3)[La(NO3)(6)], which is composed of near-spherical anions and disc-shaped ammonium cations. The confined space of (HMIm)(+) ions can be finely tuned over a broad temperature range, allowing modulation of dipolar polarization. Small-scale substitution of (HMIm)(+) ions and fine-tuning of doping ratio in the molecular solid solutions further regulate the dipole motion in the crystalline environment.