Light-Driven Adaptive Molecular Crystals Activated by [2+2] and [4+4] Cycloadditions

Photomechanical crystals act as light-driven material-machines that can convert the energy carried by photons into kinetic energy via shape deformation or displacement, and this capability holds a paramount significance for the development of photoactuated devices. This transformation is usually attributed to anisotropic expansion or contraction of the unit cell engendered by light-induced structural modifications that lead to accumulation and release of stress that generates a momentum, resulting in readily observable mechanical effects. Among the available photochemical processes, the photoinduced [2+2] and [4+4] reactions are known for their robustness, predictability, amenability to control with molecular and supramolecular engineering approaches, and efficiency that has already been elevated to a proof-of-concept smart devices based on organic crystals. This review article presents a summary of the recent research progress on photomechanical properties of organic and metal-organic crystals where the mechanical effects are based on [2+2] and [4+4] cycloaddition reactions. It consolidates the current understating of the chemical strategies and structure-property correlations, and highlights the advantages and drawbacks of this class of adaptive crystals within the broader field of crystal adaptronics.