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 =51 days at 20 °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.
Reversible photocontrol of glycosides and glycoconjugates structures is a very attractive approach to modulate, in a spatiotemporal way, the various properties and biological activities of carbohydrates. We have synthesized three new azobenzene‐derived glycomacrolactones from thioglycopyranosides. The synthesized cyclic glycoazobenzenes can be reversibly photoisomerized between E and Z isomers with high fatigue resistance. A 1H NMR spectroscopic study shows that E → Z isomerization of glycomacrocycles induces large conformational change of the macrocyclic structures, without changing sugar 4C1 chair conformation. The Z‐glycoazobenzenes can be thermally converted back to the E‐isomers. Interestingly, these 16 to 17‐membered Z‐glycomacrolactones display higher thermal stability than the reported macrocyclic azobenzenes, the half‐life varying from 37 to 72 days. The excellent photoswitching property and bistability of the synthesized glycoazobenzenes open a new opportunity for the convergent synthesis of diastereomers of glycomacrocycles. Furthermore, chiroptical properties have been observed for both E and Z glycomacrolactones. The geometry of different isomers of macrocycles has been optimized with DFT calculations. Theoretical CD spectra obtained by TD‐DFT suggest that the E and Z glycomacrocycles adopt preferentially (P) helical structure for the azobenzene moiety.
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