Anomalous structural behavior and antiferroelectricity in BiGdO3: detailed temperature and high-pressure study.

A comprehensive temperature and high-pressure investigation on BiGdO3is carried out by means of dielectric constant, piezoelectric current, polarization-electric field loop, Raman scattering and x-ray diffraction measurements. Temperature dependent dielectric constant and dielectric loss show two anomalies at about 290 K (Tr) and 720 K (TC). The latter anomaly is most likely due to antiferroelectric to paraelectric transition as hinted by piezoelectric current and polarization-electric field loop measurements at room temperature, while the former anomaly suggests reorientation of polarization. A small deviation from linear behaviour of both the Raman modes due to structural modification in the vicinity ofTC; and sharp decrease in integrated intensities of these two modes aboveTCprovide further proof for the above antiferroelectric to paraelectric transition. Cubic to monoclinic structural transition is observed at about 10 GPa in high-pressure x-ray diffraction studies accompanied by anisotropic lattice parameter changes and large unit cell volume collapse during the transition. This structural transition is corroborated by anomalous softening and large increase in full width half maximum of M2(640 cm-1) Raman mode above 10 GPa. We speculate that enhancement of large structural distortion and large reduction inc/aratio above 10 GPa might be associated with antiferroelectric to ferroelectric transition in the system.

Mechanically interlocked architecture aids an ultra-stiff and ultra-hard elastically bendable cocrystal.

Molecular crystals are not known to be as stiff as metals, composites and ceramics. Here we report an exceptional mechanical stiffness and high hardness in a known elastically bendable organic cocrystal [caffeine (CAF), 4-chloro-3-nitrobenzoic acid (CNB) and methanol (1:1:1)] which is comparable to certain low-density metals. Spatially resolved atomic level studies reveal that the mechanically interlocked weak hydrogen bond networks which are separated by dispersive interactions give rise to these mechanical properties. Upon bending, the crystals significantly conserve the overall energy by efficient redistribution of stress while perturbations in hydrogen bonds are compensated by strengthened π-stacking. Furthermore we report a remarkable stiffening and hardening in the elastically bent crystal. Hence, mechanically interlocked architectures provide an unexplored route to reach new mechanical limits and adaptability in organic crystals. This proof of concept inspires the design of light-weight, stiff crystalline organics with potential to rival certain inorganics, which currently seem inconceivable.