Acid-catalysed liquid-to-solid transitioning of arylazoisoxazole photoswitches

Kortekaas, Luuk; Simke, Julian; Arndt, Niklas B.; Böckmann, Marcus; Doltsinis, Nikos L.; Ravoo, Bart Jan

doi:10.1039/d1sc03308e

Cited by 19 publications

(20 citation statements)

References 54 publications

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“… Isomerization schemes of pH-controlled photochromism in ABs and AIZs in previous works 25 , 28 − 32 (A–C) and p -MeO-AB in this work (D). Instead of conventional acids such as HCl and CF 3 COOH, the steady states in C and D were achieved with CF 3 SO 3 H. ‡ = not observed.…”

Section: Introductionmentioning

confidence: 53%

“… 25 In recent work of our own, we reported the pH-gated photoisomerization for AIZ-derivatives, where a strong acid was added to para -alkoxy azoisoxazoles to unlock an isomerization pathway via the protonated E - and Z -isomers. 28 This latest work ultimately led us to revisit and update the pH-response of azobenzenes in the current contribution ( Figure 1 ).…”

Section: Introductionmentioning

confidence: 98%

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Reversible, Red-Shifted Photoisomerization in Protonated Azobenzenes

et al. 2022

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Azobenzenes are among the best-studied molecular photoswitches and play a key role in the search for red-shifted photoresponsive materials for extended applications. Currently, most approaches deal with aromatic substitution patterns to achieve visible light application, on occasion paired with protonation to yield red-shifted absorption of the azonium species. Appropriate substitution patterns are essential to stabilize the latter approach, as conventional acids are known to induce a fast Z - to E -conversion. Here, we show that steady-state protonation of the azo-bridge instead is possible in simple azobenzenes when the p K a of the acid is low enough, yielding both the Z - and E -azonium as supported by UV–vis- and 1 H NMR spectroscopy as well as density functional theory calculations. Moreover, the steady-state protonation of para -methoxyazobenzene, specifically, yields photoisomerizable azonium ions in which the direction of switching is essentially reversed, that is, visible light produces the out-of-equilibrium Z -azonium. Although the current conditions render the visible light photoswitch unsuitable for in vivo and material application, the demonstrated understanding of simple azobenzenes paves the way for a great range of further work on this already widely studied photoswitch.

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Section: Introductionmentioning

confidence: 53%

Section: Introductionmentioning

confidence: 98%

Reversible, Red-Shifted Photoisomerization in Protonated Azobenzenes

et al. 2022

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“…[ 25,28 ] Moreover, para‐ n ‐alkoxy‐substituted AIZ undergo a reversible photo‐induced solid‐to‐liquid phase‐transition at room temperature, as demonstrated by the group of Venkatamarani [ 29 ] as well as by us. [ 30,31 ] Our studies on the use of AIZ as reversible adhesives have shown excellent switching behavior with isomer ratios at the photostationary state of above 90%, outstanding reusability by repeated bonding and debonding due to a rapid and fast and fully reversible photo‐induced phase transition from solid E ‐AIZ to liquid Z ‐AIZ. [ 30 ] Moreover, compared to substituted azobenzenes, AIZ can be synthesized easily with excellent yields.…”

Section: Introductionmentioning

confidence: 99%

“…[ 30 ] Moreover, compared to substituted azobenzenes, AIZ can be synthesized easily with excellent yields. [ 29–31 ]…”

Section: Introductionmentioning

confidence: 99%

“…[30] Moreover, compared to substituted azobenzenes, AIZ can be synthesized easily with excellent yields. [29][30][31] Here we present a straightforward imprint method for the reversible patterning of low molecular weight para-n-alkoxysubstituted AIZ by exploiting their photo-induced phase transition at room temperature. The imprint method was developed on transparent surfaces such as glass allowing the repeated patterning of surfaces by irradiation through the surface.…”

Section: Introductionmentioning

confidence: 99%

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Versatile Surface Patterning with Low Molecular Weight Photoswitches

Meteling

Bosse

Schlichter

et al. 2022

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Surface patterning of functional materials is a key technology in various fields such as microelectronics, optics, and photonics. In micro‐ and nanofabrication, polymers are frequently employed either as photoreactive or thermoresponsive resists that enable further fabrication steps, or as functional adlayers in electronic and optical devices. In this article, a method is presented for imprint lithography using low molecular weight arylazoisoxazoles photoswitches instead of polymer resists. These photoswitches exhibit a rapid and reversible solid‐to‐liquid phase transition upon photo‐isomerization at room temperature, making them highly suitable for reversible surface functionalization at ambient conditions. Beyond photo‐induced imprint lithography with multiple write‐and‐erase cycles, prospective applications as patterned matrix for nanoparticles and etch resist on gold surfaces are demonstrated.

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Visible‐Light‐Switchable Tellurium‐Based Chalcogen Bonding: Photocontrolled Anion Binding and Anion Abstraction Catalysis

et al. 2022

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Exploring new noncovalent bonding motifs with reversibly tunable binding affinity is of fundamental importance in manipulating the properties and functions of supramolecular self‐assembly systems and materials. Herein, for the first time, we demonstrate a unique visible‐light‐switchable telluro‐triazole/triazolium‐based chalcogen bonding (ChB) system in which the Te moieties are connected by azobenzene cores. The binding strengths between these azo‐derived ChB receptors and the halide anions (Cl−, Br−) could be reversibly regulated upon irradiation by visible light of different wavelengths. The cis‐bidentate ChB receptors exhibit enhanced halide anion binding ability compared to the trans‐monodentate receptors. In particular, the telluro‐triazolium‐based ChB receptor can achieve both high and significantly photoswitchable binding affinities for halide anions, which enable it to serve as an efficient photocontrolled organocatalyst for ChB‐assisted halide abstraction in a Friedel–Crafts alkylation benchmark reaction.

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Acid-catalysed liquid-to-solid transitioning of arylazoisoxazole photoswitches

Abstract: Molecular photoswitches play a vital role in the development of responsive materials. These molecular building blocks are particularly attractive when multiple stimuli can be combined to bring about physical changes,...

Cited by 19 publications

References 54 publications

Reversible, Red-Shifted Photoisomerization in Protonated Azobenzenes

Reversible, Red-Shifted Photoisomerization in Protonated Azobenzenes

Versatile Surface Patterning with Low Molecular Weight Photoswitches

Visible‐Light‐Switchable Tellurium‐Based Chalcogen Bonding: Photocontrolled Anion Binding and Anion Abstraction Catalysis

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