Indigoid Photoswitches

Bartelmann, Thomas; Dube, Henry

doi:10.1002/9783527827626.ch13

Cited by 6 publications

(4 citation statements)

References 72 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[16][17][18][19][20][21][22] Indigoid chromophores have gained traction as intrinsically visible light responsive photoswitches for double bond isomerization reactions. [23][24][25][26] From the different variants such as indigo, [27][28][29] indirubin, 30 or thioindigo, 31 hemiindigo, 32,33 and especially hemithioindigo 25 (HTI, see also ref. [34][35][36] for some recent HTI-photoswitch examples) stand out as especially versatile core structures.…”

Section: Introductionmentioning

confidence: 99%

A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches

2023

Self Cite

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 99%

A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches

2023

Self Cite

View full text Add to dashboard Cite

show abstract

“…Stilbene , and azobenzene , based photoswitches represent probably the best-known examples, but more recently other molecular core structures such as Stenhouse adducts, , hydrazones, − imidazole-biradicals, , or hemipiperazine have emerged. Indigoid chromophores − represent another different option for double-bond isomerizing photoswitches. They undergo predictable changes in their geometry and can use visible light of different colors for both Z to E and E to Z photoisomerizations.…”

Section: Introductionmentioning

confidence: 99%

Rhodanine-Based Chromophores: Fast Access to Capable Photoswitches and Application in Light-Induced Apoptosis

Köttner,

Wolff,

Mayer

et al. 2024

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

Molecular photoswitches are highly desirable in all chemistry-related areas of research. They provide effective outside control over geometric and electronic changes at the nanoscale using an easy to apply, waste-free stimulus. However, simple and effective access to such molecular tools is typically not granted, and elaborate syntheses and substitution schemes are needed in order to obtain efficient photoswitching properties. Here we present a series of rhodanine-based photoswitches that can be prepared in one simple synthetic step without requiring elaborate purification. Photoswitching is induced by UV and visible light in both switching directions, and thermal stabilities of the metastable states as well as quantum yields are very high. An additional benefit is the hydrogen-bonding capacity of the rhodanine fragment, which enables applications in supramolecular or medicinal chemistry. We further show that the known rhodanine-based inhibitor SMI-16a is a photoswitchable apoptosis inducer. The biological activity of SMI-16a can effectively be switched ON or OFF by reversible photoisomerization between the inactive E and the active Z isomer. Rhodanine-based photoswitches therefore represent an easy to access and highly valuable molecular toolbox for implementing light responsiveness to the breadth of functional molecular systems.

show abstract

“…Molecular photoswitches enable the translation of light energy into predictable molecular changes and therefore offer precise control over the states of matter and its behavior at the smallest scales. , The field of molecular photoswitch research has grown immensely in the last decades and in addition to more traditional motives like stilbenes, , azobenzenes, or diarylethenes, − new motives, e.g., hydrazones, Stenhouse dyes, , imidazole-biradicals, , or indigoids, − have been developed more recently. In addition to this increasing diversification, classical photoswitches like azobenzenes − and diarylethenes ,− have been subject to steep developments themselves and are found in virtually every application-driven field of chemical research.…”

Section: Introductionmentioning

confidence: 99%

Reversible C═N Bond Formation Controls Charge-Separation in an Aza-Diarylethene Photoswitch

Sacherer,

Gracheva,

Maid

et al. 2024

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

Diarylethenes belong to the most eminent photoswitches and have been studied for many decades. They are found in virtually every field of application and have become highly valuable molecular tools for instilling light-responsiveness into materials, catalysts, biological systems, or pharmacology. In this work, we present a novel and distinct type of pyrimidine-based aza-diarylethene, which undergoes a highly unusual zwitterion-forming photoreaction. During this fully reversible process, a CN double bond is established under concomitant aromatization and thiophene-ring opening. The metastable zwitterion thus possesses a positively charged extended aromatic structure and an independent conjugated thiolate function. It can further photoisomerize between a more stable Z and a less stable E isomer, resulting in effective four-state photoswitching. Unusual for diarylethenes, the metastable isomers show negative solvatochromism and red-shifted absorption in apolar solvents. With this behavior, aza-diarylethenes effectively bridge the properties of merocyanines and diarylethenes. Thermal stability of the zwitterions can be modulated from very labile to highly stable behavior in response to pH, again in a fully reversible manner. Pyrimidine-based aza-diarylethene thus establishes a unique photoreaction mechanism for diarylethenes, allowing control of charge separation, thermal stability, and color generation in a different way than hitherto possible.

show abstract

Indigoid Photoswitches

Cited by 6 publications

References 72 publications

A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches

A cross-conjugation approach for high-performance diaryl-hemithioindigo photoswitches

Rhodanine-Based Chromophores: Fast Access to Capable Photoswitches and Application in Light-Induced Apoptosis

Reversible C═N Bond Formation Controls Charge-Separation in an Aza-Diarylethene Photoswitch

Contact Info

Product

Resources

About