Photoswitchable Carbohydrate-Based Macrocyclic Azobenzene: Synthesis, Chiroptical Switching, and Multistimuli-Responsive Self-Assembly
| Autor: | Juan Xie, Rémi Métivier, Stéphane Maisonneuve, Chaoqi Lin |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Circular dichroism
Macrocyclic Compounds Magnetic Resonance Spectroscopy Cyclohexane Ultraviolet Rays Carbohydrates 010402 general chemistry Photochemistry 01 natural sciences Catalysis Phase Transition chemistry.chemical_compound Photochromism Moiety Thermal stability 010405 organic chemistry Circular Dichroism Organic Chemistry Temperature Stereoisomerism General Chemistry 0104 chemical sciences Azobenzene chemistry Self-assembly Chirality (chemistry) Azo Compounds Gels |
| Zdroj: | Chemistry (Weinheim an der Bergstrasse, Germany). 23(60) |
| ISSN: | 1521-3765 |
| Popis: | 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 (t1/2=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. |
| Databáze: | OpenAIRE |
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