Temperature-Stimulus Responsive Ferroelastic Molecular–Ionic Crystal: (C8H20N)[BF4

Marcin Moskwa,Emilia Ganczar,Wojciech Medycki,Paweł Sobieszczyk,Grażyna Bator,Piotr Zieliński,Ryszard Jakubas

doi:10.1021/acs.jpcc.0c05322

Abstract

Molecular–ionic crystals, which are built of organic cations and discrete anionic components with AMX4 stoichiometry, easily induce structural order–disorder transitions. These phenomena can generate interesting ferroic properties. Herein, we have synthesized and characterized a novel AMX4-type crystal, (C8H20N)[BF4] (1). Thermal analysis, (DSC, TGA) indicates one structural phase transition (PT) at 257/259 K (cooling/heating, I ↔ II). The structure of 1 has been solved at two temperatures, 120 and 298 K, with single-crystal X-ray diffraction. The high-temperature phase I (1-HT) shows a tetragonal structure with the space group I4/mmm, whereas the low-temperature phase II (1-LT) is monoclinic with the space group P21/a. The PT belongs, thus, to the improper ferroelastic species 4/mmmF2/m with a 4-fold multiplication of the unit cell. All four possible ferroelastic domains of phase II have been identified in polarized light microscopy. The monoclinic deformation has been shown to give rise to a characteristic parquet-like texture preserving integrity of 1. The molecular mechanism of PT involving changes in the cationic and anionic dynamics has been postulated based on measurements of the 1H and 19F NMR spin–lattice relaxation times, T1, and second-moment, M2, and of the dielectric responses. The ac and dc conductivity measurements have been used to determine the transport properties of the charge carriers in 1. The intrinsic features of molecular–ionic crystals, such as the dynamics of molecular motions, structural instability with a lattice-symmetry change, formation of domain patterns, etc., provide a crystal with unique ferroelastic properties. This type of crystal may be useful as an functional material.

Highlights

One of the challenges of recent times is to obtain low-cost, stable, and ecologically friendly functional materials with useful properties for applications in modern technology
The single-crystal X-ray studies show in phase I a significant dynamic disorder of the diisobutylammonium cations and tetrafluoroborate anions
A significant change in the dynamic disorder of molecules is in accordance with the observed relatively large heat anomaly found in the calorimetry

Summary

INTRODUCTION

One of the challenges of recent times is to obtain low-cost, stable, and ecologically friendly functional materials with useful properties for applications in modern technology. An interesting scientific report by Piecha-Bisiorek et al.[31] appeared in 2015 It describes ferroic (ferroelectric and ferroelastic) properties of a molecular−ionic salt, diisobutylammonium bromide, with the unique ferroelastic structure, in which the elastic degrees of freedom gave rise to a domain pattern resembling that of martensitic phase transitions. A photosensitive organic−inorganic hybrid ferroelectric, (diisobutylammonium)3ClCoCl4,32 spontaneous polarization of approximately with a notable 4.6 μC·cm−2 and high Curie temperature (372.5 K) has been reported. In both cases, a change in dynamics of the dipolar cations leads to the generation of a spontaneous polarization. The phase transition (PT) and its concomitant phenomena have been studied here by means of the thermal, structural, electric, optical, and solid-state 1H and 19F NMR (spin−lattice relaxation time T1 and M2) measurements

EXPERIMENTAL DETAILS

RESULTS AND DISCUSSION

SUMMARY AND CONCLUSIONS

■ REFERENCES

Relaxation Dynamics and Ionic Conductivity in a Fragile Plastic