Synthesis and Characterization of Hemiindigo‐Based Glycoside and Glycomacrocycle
Abstract
As visible light responsive molecular tools, hemiindigo photoswitches are attracting increasing research interest. The development of chiral hemiindigo derivatives could expand their application fields. We synthesized the first hemiindigo‐based glycoside and glycomacrocycle in a few steps through Click reaction. These compounds can be readily photoisomerized under visible light irradiation, with a high photoconversion yield and good fatigue resistance under anaerobic conditions. Compared to the acyclic derivatives, the glycomacrocyclic hemiindigo linked through N ‐substitution on the indoxyl moiety displayed a constrained molecular geometry, significantly modifying the shape of the absorption band in the visible. The hemiindigo glycomacrocyle also exhibited more efficient Z ⇄ E photoisomerization compared to its acyclic counterpart, with a two‐fold increase of the photochromic quantum yield (0.34 for Φ Z → E and 0.12 for Φ E → Z ). These observed specific photophysical behaviors were rationalized using DFT and TD‐DFT calculations. The most twisted E‐ macrocycle displayed chiroptical activity, allowing an on‐off chiroptical switching upon Z → E → Z photoisomerization. All of the investigated hemiindigo derivatives exhibited fluorescence in their Z ‐form.
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BibTeX
@article{fontaine2026synthesis,
title = {{Synthesis and Characterization of Hemiindigo‐Based Glycoside and Glycomacrocycle}},
author = {Guilhem Fontaine and Rémi Métivier and Guillaume Laurent and Régis Guillot and Juan Xie},
journal = {Chemistry - A European Journal},
year = {2026},
month = oct,
doi = {10.1002/chem.71764},
url = {https://hal.science/hal-05788984v1},
note = {CC BY-NC-ND},
}
RIS
TY - JOUR
TI - Synthesis and Characterization of Hemiindigo‐Based Glycoside and Glycomacrocycle
AU - Guilhem Fontaine
AU - Rémi Métivier
AU - Guillaume Laurent
AU - Régis Guillot
AU - Juan Xie
PY - 2026
DA - 2026/10/05
JO - Chemistry - A European Journal
DO - 10.1002/chem.71764
UR - https://hal.science/hal-05788984v1
AB - As visible light responsive molecular tools, hemiindigo photoswitches are attracting increasing research interest. The development of chiral hemiindigo derivatives could expand their application fields. We synthesized the first hemiindigo‐based glycoside and glycomacrocycle in a few steps through Click reaction. These compounds can be readily photoisomerized under visible light irradiation, with a high photoconversion yield and good fatigue resistance under anaerobic conditions. Compared to the acyclic derivatives, the glycomacrocyclic hemiindigo linked through N ‐substitution on the indoxyl moiety displayed a constrained molecular geometry, significantly modifying the shape of the absorption band in the visible. The hemiindigo glycomacrocyle also exhibited more efficient Z ⇄ E photoisomerization compared to its acyclic counterpart, with a two‐fold increase of the photochromic quantum yield (0.34 for Φ Z → E and 0.12 for Φ E → Z ). These observed specific photophysical behaviors were rationalized using DFT and TD‐DFT calculations. The most twisted E‐ macrocycle displayed chiroptical activity, allowing an on‐off chiroptical switching upon Z → E → Z photoisomerization. All of the investigated hemiindigo derivatives exhibited fluorescence in their Z ‐form.
SN - 0947-6539
SN - 1521-3765
ER -