Photoswitchable Carbohydrate-Based Macrocyclic Azobenzene: Synthesis, Chiroptical Switching, and Multistimuli-Responsive Self-Assembly

A one-pot O-alkylation mediated macrocyclization approach has been used for the synthesis of carbohydrate-based macrocyclic azobenzene. The synthesized macrocycle can be reversibly isomerized between E and Z isomers upon UV or visible irradiation with excellent photostability and thermal stability (t(1/2)=51days at 20 degrees C for the Z isomer). A chirality transfer from the chiral sugar unit to azobenzene was observed by circular dichroism (CD). DFT and TD-DFT calculations were performed to calculate the optimal geometry and the theoretical absorption and CD spectra. Comparison of the experimental CD spectra with the theoretical ones suggests that both E- and Z-macrocycles adopt preferentially P-helicity for the azobenzene moiety. Furthermore, the macrocycle showed gelation ability in cyclohexane and ethanol with multistimuli-responsive behavior upon exposure to environmental stimuli including thermal-, photo-, and mechanical responses. Moreover, these organogels display temperature-dependent helical inversion, which can be tuned by a repeated heating-cooling procedure.