Main-chain stiff-stilbene photoswitches in solution, in bulk, and at surfaces†

Molecular photoswitches have been incorporated into polymer backbones to control the macromolecular conformations by structural changes of the main-chain photoswitches. However, previous photoswitches installed in the main chains are thermolabile, which precludes deep understanding, precise regulation, and practical applications of the macromolecular conformational changes. Herein, we focus on sterically hindered stiff stilbene (HSS), an emerging photoswitch offering large structural changes in isomerization between the thermally bistable E and Z isomers, and disclose the chemistry of main-chain HSS photoswitches in solution, in bulk, and at thin film surfaces. We synthesize and investigate three types of linear polymers with different chemical linkages between HSS repeating units, polyurethane, polyester, and polyene. The polymer conformations in solution, i.e., hydrodynamic volume, are reversibly photocontrollable in a precise manner by the E/Z ratio. Furthermore, the nanoscopic conformational transformations are amplified to macroscopic photoswitching of the solution transmittance and the surface wettability synergistically with changes between interchain and intrachain hydrogen bonding in the polyurethanes. Additionally, the Z-to-E photoisomerization yields in the glassy state are above 70%, comparable to those in solution, and extraordinarily high despite the restricted molecular mobility. The findings of this study will pave the way for practical and unconventional applications of smart polymer systems based on photoswitches.