An Azobenzene Unit Embedded in a Cyclopeptide as a Type‐Specific and Spatially Directed Switch

Haberhauer, Gebhard; Kallweit, Christine; Wölper, Christoph; Bläser, Dieter

doi:10.1002/anie.201301516

Cited by 32 publications

(20 citation statements)

References 53 publications

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“…The CD spectrum at PSS 435 represents an average between E and Z isomers CD spectra (cyan line). It has been reported that azobenzene could generate P or M helical chirality –. We have firstly optimized the geometry of E ‐( P )‐ 1 , E ‐( M )‐ 1 , Z ‐( P )‐ 1 , and Z ‐( M )‐ 1 by using B3LYP/6‐311G functional and basis set (Figure and Figure S11 in the Supporting Information).…”

Section: Methodsmentioning

confidence: 99%

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

Lin

Maisonneuve

Métivier

et al. 2017

Chemistry A European J

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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.

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Section: Methodsmentioning

confidence: 99%

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

Lin

Maisonneuve

Métivier

et al. 2017

Chemistry A European J

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“…This result is important because it also suggests that the trans → cis isomerization of the photoresponsive hinge may occur following an unidirectional motion, as it has been demonstrated by Haberhauer et al. in the case of azobenzenes clamped with small cyclo‐peptide scaffolds ,…”

Section: Resultsmentioning

confidence: 99%

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

Despras

Hain

Jaeschke

2017

Chemistry A European J

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Reversible shape switching due to external stimuli is an attractive property for the control of molecular features. Hence, we aimed at macrocycles to investigate photoswitching of molecular shape. We prepared the first carbohydrate-based macrocycles comprising a photoresponsive azobenzene hinge. These macrocycles were readily obtained by cyclization of isothiocyanate-armed bis-azobenzene glycosides with piperazine. The unprotected macrocycles exhibit favorable photochromic properties in water and DMSO. Notably, the efficient trans→cis isomerization results in a remarkable shape transformation of the molecule. Additionally, the structure is characterized by restricted conformational freedom of the backbone, resulting in a single main conformer in each geometrical state (trans or cis). Measurement of optical rotation values and circular dichroism spectra revealed a tremendous change in chirality upon photoisomerization, with a strong helical induction in the cis state. These findings highlight the applicability of the new macrocycles as chiroptical molecular switches.

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“…Azobenzene and its derivatives can undergo reversible trans-cis isomerization upon irradiation with UV or visible light at certain wavelength [4][5][6]. Induced by the reversible change of molecular shape of azobenzene moiety, azopolymers demonstrate a variety of photoresponsive properties, and result in a number of practical applications, such as optical information storage [7,8], actuators [9,10], surface gratings [11][12][13], light-driven molecular switches [14,15], sustained-release drugs [16][17][18], light-controlled microfluidics and other photonic devices [19][20][21][22].…”

Section: Introductionmentioning

confidence: 99%

Influence of Chromophoric Electron-Donating Groups on Photoinduced Solid-to-Liquid Transitions of Azopolymers

Niu

Guo

et al. 2020

Polymers

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The photoinduced solid-to-liquid transitions property of azobenzene-containing polymers (azopolymers) enables azopolymers with various promising applications. However, a general lack of knowledge regarding the influence of structure of the azobenzene derivatives on the photoinduced liquefaction hinders the design of novel azopolymers. In the present study, a series of azopolymers with side chains containing azobenzene unit bearing alkyl electron-donating groups were synthesized. The photoisomerization and photoinduced liquefaction properties of newly synthesized azopolymers were investigated. Alkyl-based electron-donating group significantly facilitate the photoisomerization process of azopolymers in solution, as the electron-donating ability of substituents increased, the time required for photoisomerization of azopolymers continually deceased. Meanwhile, the electron-donating group can drastically accelerate photoinduced solid-to-liquid transitions of azopolymers, the liquefaction rate of obtained azopolymers gradually getting quicker as the electron-donating ability of substituents increased. This study clearly demonstrates that the electron-donating group that bearing in the azobenzene group of polymer side chain play an essential role on the photoinduced solid-to-liquid transitions of azopolymers, and hence, gives an insight into how to design novel azopolymers for practical applications.

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An Azobenzene Unit Embedded in a Cyclopeptide as a Type‐Specific and Spatially Directed Switch

Cited by 32 publications

References 53 publications

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

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

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

Influence of Chromophoric Electron-Donating Groups on Photoinduced Solid-to-Liquid Transitions of Azopolymers

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