Photocontrol over Molecular Shape: Synthesis and Photochemical Evaluation of Glycoazobenzene Macrocycles

Despras, Guillaume; Hain, Julia; Jaeschke, Sven Ole

doi:10.1002/chem.201701232

Cited by 23 publications

(20 citation statements)

References 128 publications

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“…Jaeschke and co-workers [ 283 ] described carbohydrate-based macrocycles obtained from isothiocyanate-armed bis-azobenzene glycosides and piperazine. Isomerization of glycoazobenzene precursor molecules before the reaction ensured more efficient macrocyclization (yields: 48–65%).…”

Section: Miscellaneous Macrocyclic Systems Bearing Azo Group(s)mentioning

confidence: 99%

Azo group(s) in selected macrocyclic compounds

Wagner‐Wysiecka

Łukasik

Biernat

et al. 2018

J Incl Phenom Macrocycl Chem

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Azobenzene derivatives due to their photo- and electroactive properties are an important group of compounds finding applications in diverse fields. Due to the possibility of controlling the trans–cis isomerization, azo-bearing structures are ideal building blocks for development of e.g. nanomaterials, smart polymers, molecular containers, photoswitches, and sensors. Important role play also macrocyclic compounds well known for their interesting binding properties. In this article selected macrocyclic compounds bearing azo group(s) are comprehensively described. Here, the relationship between compounds’ structure and their properties (as e.g. ability to guest complexation, supramolecular structure formation, switching and motion) is reviewed.

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Section: Miscellaneous Macrocyclic Systems Bearing Azo Group(s)mentioning

confidence: 99%

Azo group(s) in selected macrocyclic compounds

Wagner‐Wysiecka

Łukasik

Biernat

et al. 2018

J Incl Phenom Macrocycl Chem

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“…The 17‐membered gluco Z ‐macrocycle 2 showed the highest stability. It's to be noticed that the two 28‐membered Z ‐glycomacrocycles as well as the 38‐membered one reported by G. Despras et al displayed much shorter half‐life time ( τ 1/2 = 6.2, 114 and 17.2 h respectively) , . Binaphthyl linked 18‐ to 30‐membered azobenzene macrocycles showed the half‐life varied from 3.5 to 12 days, while the 18‐membered cyclic naphthyl Z ‐azobenzene was less stable ( τ 1/2 = 2.5 h) .…”

Section: Resultsmentioning

confidence: 95%

“…Natural and synthetic glycomacrocycles, especially carbohydrate‐based macrolactones, have shown various interesting properties in chemistry and biology Photoswitchable glycomacrocycles have also been very recently developed . The glycoazobenzene macrocycles developed by G. Despras et al, with the 4,4′‐dihydroxyazobenzene linked to the anomeric or O 6 ‐position of the sugar units, allowed the photocontrol over molecular shape , . A chirality transfer from sugar to azobenzene part has also been observed.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Photochromic Properties of Azobenzene‐Derived Glycomacrolactones

et al. 2019

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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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“…Moreover, the azobenzene-based macrocyclic molecule was designed to change the optical chirality dramatically and to avoid multi-conformation of a single trans-or cis-isomer during photoisomerization. [104][105][106][107] Such macrocyclic materials were synthesized through cyclization between the azobenzene derivatives and chiral sugars ( Figure 8E-a), which transferred the chirality to the mesogenic azobenzene moiety, enabling significant CD modulation of not only the absorption, but also the sign of the Cotton band (i.e., the chirality of the material) ( Figure 8E-b). In addition, such macrocyclic materials exhibited the gel state in cyclohexane and ethanol, with interconversion between gel and sol through diverse stimuli, including light, temperature, and mechanical force.…”

Section: Photoresponsive Gelsmentioning

confidence: 99%

Photoprogrammable Mesogenic Soft Helical Architectures: A Promising Avenue toward Future Chiro‐Optics

Zheng

2020

Advanced Materials

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reflection, exhibits photonic localization in the band gap determined by the period in the case of normal incidence. [6] Similarly, a helical superstructure composed of chiral chromophores leads to absorption differences between left-and right-handed CPL, referred to as the Cotton effect, owing to the asymmetry of chiral chromophores or that of achiral chromophores induced by a chiral system. [7] Chiro-optical characteristics in helical supramolecular assemblies and superstructures have attracted tremendous attention in the past decade, especially in self-organized mesogenic helical soft matter, which is an emerging scientific frontier in chemistry, functional materials, soft matter physics, biological medicine, and even sensor physics. Mesogenic soft matter, defined as soft condensed matter with molecules containing single or multiple anisotropic mesogen moieties, is distinct from common soft condensed matter in terms of molecular arrangement, interaction, and specific optical chirality, although the "soft" characteristic is still maintained. A primary reason for the softness is related to the responses of this type of matter to multiple external stimuli, such as electric fields, heat, light, mechanical forces, and even acoustic fields. [8] The control and manipulation of such soft materials by light is always more desirable than that of other stimuli due to the prominent advantages of non-contact, wireless, remote, and high-resolution control, which enable numerous unprecedented chiro-optical applications. [9] Optically, another fascinating feature of these materials is their molecular self-organization behavior, which can establish an ordered and regular arrangement with a structural parameter (≈µm) much larger than the single-molecule scale (≈nm) through the weak non-covalent molecular interaction, rather than the chemical bonds that normally exist in

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Photocontrol over Molecular Shape: Synthesis and Photochemical Evaluation of Glycoazobenzene Macrocycles

Cited by 23 publications

References 128 publications

Azo group(s) in selected macrocyclic compounds

Azo group(s) in selected macrocyclic compounds

Synthesis and Photochromic Properties of Azobenzene‐Derived Glycomacrolactones

Photoprogrammable Mesogenic Soft Helical Architectures: A Promising Avenue toward Future Chiro‐Optics

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