Fast E/Z UV-light response T-type photoswitching of phenylene-thienyl imines

Veselý, Dominik; Jančík, Ján; Weiter, Martin; Blasi, Davide; Ivanova, Nikoleta; Krajčovič, Jozef; Georgiev, Anton

doi:10.1016/j.jphotochem.2022.113994

Cited by 7 publications

(4 citation statements)

References 57 publications

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“…It is well-known that azomethines, known photoswitches, , can undergo photoisomerization, where ( E )-to-( Z ) conformational changes result in a loss of fluorescence signal due to twisted intramolecular charge transfer (TICT) in the ( Z )-conformation . The effect of the FA concentration on the kinetics of Az-H photoisomerization was accordingly probed in solution.…”

Section: Resultsmentioning

confidence: 99%

“…Interconversion of (E)-and (Z)-Az-H with Forward and Reverse Rates (k 1 and k −1 , Respectively) photoswitches, 27,28 can undergo photoisomerization, where (E)-to-(Z) conformational changes result in a loss of fluorescence signal due to twisted intramolecular charge transfer (TICT) in the (Z)-conformation. 27 The effect of the FA concentration on the kinetics of Az-H photoisomerization was accordingly probed in solution. For these experiments, a high photon flux, 365 nm LED lamp was used as the excitation source.…”

Section: Az-h Absorbance and Fluorescence Features Are Significantly ...mentioning

confidence: 99%

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An Azomethine-H-Based Fluorogenic Sensor for Formic Acid

Potter,

Debnath,

Drover

et al. 2023

ACS Appl. Mater. Interfaces

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Formic acid (FA) is an important C 1 -containing feedstock that serves as a masked source of dihydrogen gas (H 2 ). To encourage the adoption of cleaner (noncarbonaceous) energy sources, FA detection and sensing is thus of considerable interest. Here, we examine the use of a commercially available dye, azomethine-H (Az-H), for FA sensing. Solution studies confirm that FA quenches both the absorbance and the luminescence properties of Az-H. FA was additionally found to attenuate a known Az-H (E)-to-(Z) conformational change, suggesting an Az-H/FA interaction, possibly through hydrogen bonding; this phenomenon was probed using 1 H NMR spectroscopy. Moving toward a solidstate sensor, the Az-H probe was incorporated into a gelatin-based matrix. On exposure to FA, the luminescence of this system was found to increase in a FA-dependent manner, attributed to the formation of stable hydrogen-bonded structures, facilitating a (Z)-to-(E) isomerization via imine protonation, allowing for production of the more luminescent (E)-isomer. This fluorogenic signal was used as a FA sensor with an estimated detection limit of ca. 0.4 ppb FA vapor. This work constitutes an important step toward a highly sensitive FA sensor in both the solution and solid state, opening new space for the detection of organic acids in differing chemical environments.

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Section: Resultsmentioning

confidence: 99%

Section: Az-h Absorbance and Fluorescence Features Are Significantly ...mentioning

confidence: 99%

An Azomethine-H-Based Fluorogenic Sensor for Formic Acid

Potter,

Debnath,

Drover

et al. 2023

ACS Appl. Mater. Interfaces

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show abstract

“…1a). These properties include: (i) short thermal half-lives (t 1/2 ) 37,38 that typically range from 10 −3 to 10 1 s at room temperature (Table S3 †); (ii) low completeness of photoswitching to the metastable state at the photostationary state (PSS, <50%, Table S3 †); (iii) the need for high energy UV light to induce photoisomerism, typically in the range of 254 to 365 nm. 30 Overcoming these limitations would expand the toolkit of available photochromic compounds and enable the creation of new dynamic-covalent materials 39,40 that responds to light directly at the imine bond.…”

Section: Introductionmentioning

confidence: 99%

Photoswitchable imines: aryliminopyrazoles quantitatively convert to long-lived Z-isomers with visible light

Wu,

Kreimendahl,

Tao

et al. 2024

Chem. Sci.

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“…23,29 This is attributed to their poor photoswitching properties, rendering them challenging systems to study (Figure 1a). These properties include: (i) short thermal half-lives (t1/2) 30,31 that typically range from 10 −3 to 10 1 s at room temperature (Table S3); (ii) low completeness of photoswitching to the metastable state at the photostationary state (PSS, <50%, Table S3); (iii) the need for high energy UV light to induce photoisomerism, typically in the range of 254 to 365 nm. 23 Overcoming these limitations would expand the toolkit of available photochromic compounds and enable the creation of new dynamic-covalent materials that responds to light directly at the imine bond.…”

Section: Introductionmentioning

confidence: 99%

Photoswitchable Imines: Aryliminopyrazoles Quantitatively Convert to Long-Lived Z-Isomers with Visible Light

Wu,

Kreimendahl,

Tao

et al. 2023

Preprint

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Arylimines offer promise in dynamic-covalent materials due to their recyclability and ease of synthesis. However, their light-triggered E/Z isomerism has received little attention. This is attributed to challenges that include low thermal stability of their metastable state (<60 s at 20 °C), incomplete photoswitching (<50% to the metastable state), and the need for UV light (≤365 nm). We overcome these limitations with a novel class of imine photoswitch, the aryliminopyrazoles (AIPs). These AIPs can be switched using visible light (470 nm), attain photostationary states with over 95% of the Z-isomer, exhibit great resistance to fatigue, and have thermal half-lives up to 19.2 hours at room temperature. Additionally, they display T-type and negative photochromism under visible light irradiation—a useful property. The quantitative assembly, accessibility of precursors, and recyclability set these photoswitches apart from their azo-based analogues. These findings open avenues for next-generation photoresponsive dynamic-covalent materials driven solely by these new photochromic linkages and further exploration of photocontrolled dynamic combinatorial chemistry.

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Fast E/Z UV-light response T-type photoswitching of phenylene-thienyl imines

Cited by 7 publications

References 57 publications

An Azomethine-H-Based Fluorogenic Sensor for Formic Acid

An Azomethine-H-Based Fluorogenic Sensor for Formic Acid

Photoswitchable imines: aryliminopyrazoles quantitatively convert to long-lived Z-isomers with visible light

Photoswitchable Imines: Aryliminopyrazoles Quantitatively Convert to Long-Lived Z-Isomers with Visible Light

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