Arylazobenzimidazoles: versatile visible-light photoswitches with tuneable <i>Z</i>-isomer stability

Steinmüller, Sophie A. M.; Odaybat, Magdalena; Galli, Giulia; Prischich, Davia; Fuchter, Matthew J.; Decker, Michael

doi:10.1039/d3sc05246j

Cited by 6 publications

(2 citation statements)

References 61 publications

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“…Mono-heteroaryl azoswitch (Het-NN-Ph) is a highly adaptable molecular architecture, which allows visible-light photoswitching to be achieved by selecting electron-rich heterocycles or introducing p-electron-donating substituents at the phenyl ring. Relative to that of azobenzene ( 1 ) (λ max = 317 nm), mono-heteroaryl azoswitches bearing electron-rich heterocycles such as 5-pyrazole, 2-thiophene, , 2-imidazole, , 2-thiazole, 3-indole, benzimidazole and 2-pyrrole , exhibited red-shifted π–π* bands (π–π* λ max between 340 and 390 nm, Figure ). These red-shifts can be explained by extended conjugation involving the lone-pair electrons of heteroatoms or fused-ring.…”

Section: Mono-heteroaryl Azoswitchesmentioning

confidence: 99%

“…Photoswitch properties of azobenzene , and typical mono-heteroaryl azoswitches bearing electron-rich heterocycles including 4-pyrazole, 5-pyrazole, 2-thiophene, 2-imidazole, 2-thiazole, 3-indole, benzimidazole and 2-pyrrole . The electron-rich nature of these heterocycles is derived from plausible resonance structures, where lone-pair electrons drift from the heteroatom toward the ring carbons, leading to partial negative charges on the carbon atoms.…”

Section: Mono-heteroaryl Azoswitchesmentioning

confidence: 99%

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Visible-Light-Activated Heteroaryl Azoswitches: Toward a More Colorful Future

Dang,

Zhang,

2024

J. Am. Chem. Soc.

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Azobenzenes (Ph-N�N-Ph) are known as the most widely studied molecular photoswitches, and the recent rise of azoheteroarenes (Het-N�N-Ph or Het-N�N-Het) offers great opportunities to advance this already mature field. A common limitation is that azo-switches generally require harmful UV light for activation, which hinders their application across various fields. Despite great efforts in developing visible-light azobenzenes over the past few decades, the potential of visible-light heteroaryl azoswitches remains largely unexplored. This Perspective summarizes the state-of-the-art advancements in visible-light heteroaryl azoswitches, covering molecular design strategies, the structure−property relationship, and potential applications. We highlight the distinctive advantages of azoheteroarenes over azobenzenes in the research and development of visible-light switches. Furthermore, we discuss the opportunities and challenges in this emerging field and propose potential solutions to address crucial issues such as spectral red-shift and thermal half-life. Through this Perspective paper, we aim to provide inspiration for further exploration in this field, in anticipation of the growing prosperity and bright future of visible-light azoheteroarene photoswitches.

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Section: Mono-heteroaryl Azoswitchesmentioning

confidence: 99%

Section: Mono-heteroaryl Azoswitchesmentioning

confidence: 99%

Visible-Light-Activated Heteroaryl Azoswitches: Toward a More Colorful Future

Dang,

Zhang,

2024

J. Am. Chem. Soc.

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Progress of Photoantibiotics in Overcoming Antibiotic Resistance

Bhunia,

Box,

Bera

et al. 2024

ChemMedChem

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Antibiotic resistance has emerged as a global public health crisis in the 21st century, leading to treatment failures. To address this issue, the medical and pharmaceutical sectors are confronted with two challenges: i) finding potent new antimicrobial agents that would work against resistant–pathogens, and ii) developing conceptually new or unconventional strategies by which a particular antibiotic would remain effective persistently. Photopharmacology with the aid of reversibly controllable light‐active antibiotics that we call “photoantibiotics” shows great promise to meet the second challenge, which has inspired numerous research laboratories worldwide to align their research in inventing or developing such antibiotics. In this review, we have given an overview of the progress made over the last ten years or so towards developing such photoantibiotics. Although making such antibiotics that hold high antimicrobial potency like the native drugs and subsequently maintain a significant activity difference between light irradiated and non‐irradiated states is very challenging, the progress being reported here demonstrates the feasibility of various approaches to engineer photoantibiotics. This review provides a future perspective on the use of such antibiotics in clinical practice with the identification of potential problems and their solutions.

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Photoswitching Characteristics, Photochromism and Mechanochromism of Extended π‐Conjugated Azopyrazole and Azoisoxazole Derivatives

Kumar,

Nasare,

Parthiban

et al. 2024

ChemPhotoChem

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Herein, we report extended π‐conjugated arylazopyrazoles and arylazoisoxazoles towards tuning and modulation of their intrinsic properties. In this regard, we systematically introduced phenyl, styryl, (triphenylvinyl)styryl, phenylethynyl groups at ortho, meta, and para positions relative to the azo unit to extend the π‐conjugation and vary the electronic coupling. In addition, the heterocyclic substituents were also modified. Overall, 20 photoswitches with modular substituents have been synthesized and studied for the photoswitching ability and thermal relaxations of Z isomers in the solution phase and solid state. Besides deciphering the importance of extending conjugation in photoswitching characteristics, intriguing properties such as mechanochromism and reversible bidirectional photochromism in the solid state were also unravelled. Through systematic studies, we envisage the effect of electronic coupling due to π‐conjugation and its impact on longer wavelength light‐induced photoswitching that holds several application potentials.

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Arylazobenzimidazoles: versatile visible-light photoswitches with tuneable Z-isomer stability

Abstract: Benzimidazole heterocycles are of great importance in medicinal chemistry due to their applicability to a wide range of pharmacological targets, therefore representing a prototypical “privileged structure”. In photopharmacology, azoheteroarene photoswitches...

Cited by 6 publications

References 61 publications

Visible-Light-Activated Heteroaryl Azoswitches: Toward a More Colorful Future

Visible-Light-Activated Heteroaryl Azoswitches: Toward a More Colorful Future

Progress of Photoantibiotics in Overcoming Antibiotic Resistance

Photoswitching Characteristics, Photochromism and Mechanochromism of Extended π‐Conjugated Azopyrazole and Azoisoxazole Derivatives

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