In the last century, molecular crystals functioned predominantly as a means for determining the molecular structures via X-ray diffraction, albeit as the century came to a close the response of molecular crystals to electric, magnetic, and light fields revealed that the physical properties of molecular crystals were as rich as the diversity of molecules themselves. In this century, the mechanical properties of molecular crystals have continued to enhance our understanding of the colligative responses of weakly bound molecules to internal frustration and applied forces. Here, the authors review the main themes of research that have developed in recent decades, prefaced by an overview of the particular considerations that distinguish molecular crystals from traditional materials such as metals and ceramics. Many molecular crystals will deform themselves as they grow under some conditions. Whether they respond to intrinsic stress or external forces or interactions among the fields of growing crystals remains an open question. Photoreactivity in single crystals has been a leading theme in organic solid-state chemistry; however, the focus of research has been traditionally on reaction stereo- and regio-specificity. However, as light-induced chemistry builds stress in crystals anisotropically, all types of motions can be actuated. The correlation between photochemistry and the responses of single crystals—jumping, twisting, fracturing, delaminating, rocking, and rolling—has become a well-defined field of research in its own right: photomechanics. The advancement of our understanding requires theoretical and high-performance computations. Computational crystallography not only supports interpretations of mechanical responses, but predicts the responses itself. This requires the engagement of classical force-field based molecular dynamics simulations, density functional theory-based approaches, and the use of machine learning to divine patterns to which algorithms can be better suited than people. The integration of mechanics with the transport of electrons and photons is considered for practical applications in flexible organic electronics and photonics. Dynamic crystals that respond rapidly and reversibly to heat and light can function as switches and actuators. Progress in identifying efficient shape-shifting crystals is also discussed. Finally, the importance of mechanical properties to milling and tableting of pharmaceuticals in an industry still dominated by active ingredients composed of small molecule crystals is reviewed. A dearth of data on the strength, hardness, Young's modulus, and fracture toughness of molecular crystals underscores the need for refinement of measurement techniques and conceptual tools. The need for benchmark data is emphasized throughout.

Being capable of rapid and complete structure switching, the martensitic phase transitions in molecular crystals are thought to hold a tremendous potential as thermally driven organic actuators. However, the mechanical engineering parlance in the assessment of their performance is not immediately legible to the chemistry research community that starts to explore these materials, and the unavailability of performance indices has precluded molecular crystals from being considered in the device design process. Here, we demonstrate that an organic martensite, hexamethylbenzene, can be used to perform work that is comparable to that of most actuator classes. Millimeter-size single crystals of this material undergo a transition between two forms by uniaxial expansion at a rate of 6.36(2) mm s⁻¹, exerting force in the range 10–100 mN. The force-to-weight ratio of the crystals is on the order of 10⁴ and is superior to that of some living creatures. An actuator performance chart reveals that the performance of this material is close to that of nanomuscles, electrostatic actuators and voice coils, with a strain higher than that of electro/magnetostrictive actuators and ceramic piezoelectrics and stress higher than that of the electroactive polymers, MEMS devices, nanomuscles, voice coils, and some solenoids. Moreover, the crystals of this material are mechanically compliant and can be reversibly bent and shaped to fit the desired application. Altogether, the results point to the untapped potential of molecular crystals as rapid and efficient soft, organic actuators.

Organic crystal is described that can be bent plastically and twisted elastically, and can self-heal to 67%, an efficiency that is an order-of-magnitude higher compared to the only previously reported example.