Thermally Stable Photomechanical Molecular Hinge: Sterically Hindered Stiff-Stilbene Photoswitch Mechanically Isomerizes.

Abstract

Molecular photoswitches are extensively used as molecular machines because of the small structures, simple motions, and advantages of light including high spatiotemporal resolution. Applications of photoswitches depend on the mechanical responses, in other words, whether they can generate motions against mechanical forces as actuators or can be activated and controlled by mechanical forces as mechanophores. Sterically hindered stiff stilbene (HSS) is a promising photoswitch offering large hinge-like motions in the E/Z isomerization, high thermal stability of the Z isomer, which is relatively unstable compared to the E isomer, with a half-life of ca. 1000 years at room temperature, and near-quantitative two-way photoisomerization. However, its mechanical response is entirely unexplored. Here, we elucidate the mechanochemical reactivity of HSS by incorporating one Z or E isomer into the center of polymer chains, ultrasonicating the polymer solutions, and stretching the polymer films to apply elongational forces to the embedded HSS. The present study demonstrated that HSS mechanically isomerizes only in the Z to E direction and reversibly isomerizes in combination with UV light, i.e., works as a photomechanical hinge. The photomechanically inducible but thermally irreversible hinge-like motions render HSS unique and promise unconventional applications differently from existing photoswitches, mechanophores, and hinges.