A Temperature-Stimulus Responsive Ferroelastic Molecular-Ionic Crystal: (C8H20N)[BF4]
2020
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.
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