Negative to Positive Axial Thermal Expansion Switching of an Organic Crystal: Contribution to Multistep Photoactuation

Materials displaying negative thermal expansion (NTE), in contrast to typical materials with positive thermal expansion (PTE), are attractive for both fundamental research and practical applications, including the development of composites with near-zero thermal expansion. A recent data mining study revealed that approximately 34% of organic crystals may present NTE, indicating that NTE in organic crystals is much more common than generally believed. However, organic crystals that switch from NTE to PTE or have rarely been reported. Here, we report the crystal of -3,5-di--butylsalicylide-3-nitroaniline in the enol form (enol-1) as the first organic crystal in which the axial thermal expansion changes from negative to positive at around room temperature. When heated, the crystal shrinks along the -axis below 30 °C and then it expands above 30 °C. Geometric calculations revealed that below 30 °C, the decrease in the tilt angle of the molecule exceeds the increase in the interplanar distance, causing NTE, whereas above 30 °C, the increase in the interplanar distance outweighs the decrease in the tilt angle, resulting in PTE. By combining photoisomerisation and the NTE-PTE switching induced by the photothermal effect, multistep crystal photoactuation was achieved. Moreover, actuation switching of the same crystal sample by changing atmosphere temperature was realised by utilising the NTE-PTE change. Such NTE-PTE switching without a thermal phase transition provides not only new insight into organic crystals but also a new strategy for designing crystal actuators.