A role of intermolecular interaction modulating thermal diffusivity in organosuperelastic and organoferroelastic cocrystals

Although the finding of superelasticity and ferroelasticity in organic crystals has been serendipitous, an increasing number of organic crystals with such deformation properties have been witnessed. Understanding the structure-property relationship can aid in the rational selection of intermolecular interactions to design organic crystals with desired superelastic or ferroelastic properties. In this study, we investigated the mechanical deformation in two cocrystals, prepared with the parent compound, 1,4-diiodotetrafluorobenzene with two coformers, 1,2-bis(4-pyridyl)ethane and pyrene. The parent compound and coformers were chosen to introduce distinct weak interactions such as halogen bonds and C-HMIDLINE HORIZONTAL ELLIPSISF, and pi MIDLINE HORIZONTAL ELLIPSIS pi interactions in the crystal structure. The two cocrystals exhibited different mechanical deformations, superelasticity, and ferroelasticity, respectively. The single-crystal X-ray diffraction and energy framework analysis of the crystal structure of the cocrystals revealed that both deformations were caused by mechanical twinning. Interestingly, a difference in the extent of deformation was observed, modulated by a combination of strong and weak intermolecular interactions in the superelastic cocrystal, and only weak interaction in the ferroelastic one. In this comparison, the superelastic cocrystal exhibited higher thermal diffusivity than the ferroelastic cocrystal, indicating the presence of symmetrical and relatively robust intermolecular interactions in the superelastic cocrystal. Anisotropic thermal diffusivity correlates with the intermolecular interactions in two cocrystals with varying halogen acceptor abilities, which also influenced the superelastic and ferroelastic behaviour.

Automated summary

This study investigates the mechanical deformation in two cocrystals and reveals the relationship between structure and properties, providing guidance for the design of organic crystals with superelastic or ferroelastic properties based on rational selection of intermolecular interactions.