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.

Block-like microcrystals composed of cis-dimethyl-2(3-(anthracen-9-yl)allylidene)malonate are grown from aqueous surfactant solutions. A pulse of 405 nm light converts a fraction of molecules to the trans isomer, creating an amorphous mixed layer that peels off the parent crystal. This photoinduced delamination can be repeated multiple times on the same block.

(E)-4-Fluoro-cinnamaldehyde malononitrile ((E)-4FCM) is a new phenylbutadiene derivative that undergoes a [2+2] photocycloaddition in the crystal form. Optical absorption and proton nuclear magnetic resonance (¹H-NMR) measurements demonstrate that the solid-state (E)-4FCM photodimerization is a negative photochromic reaction that proceeds to 97% completion. The large geometry change and full conversion allow bulk crystals of (E)-4FCM to show strong photosalient effects when exposed to 405 nm ultraviolet light. When (E)-4FCM nanowires are grown in an anodic alumina oxide (AAO) template, they maintain a high degree of crystallinity and orientation, as determined by X-ray diffraction measurements. When illuminated, (E)-4FCM nanowire bundles exhibit a rapid expansion, during which they spread by as much as 300% in the lateral direction. This lateral expansion is at least partially due to a photoinduced crystal expansion along the diameter of the nanowires. When (E)-4FCM nanowires are confined inside the AAO template, the photoinduced expansion can be harnessed to deform the template, causing it to bend under UV light irradiation. The bending motion due to 2.0 mg of 4FCM in a template can cause the template to bend by up to 1.0 mm and lift up to 200 g. These results represent a significant improvement in work output relative to previous composite actuator membranes based on diarylethene photochromes.