Diaryl-hemiindigos as visible light, pH, and heat responsive four-state switches and application in photochromic transparent polymers

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: July 20, 2023

Photoswitches are indispensable tools for responsive chemical nanosystems and used today in almost all areas of the natural sciences. Hemiindigo (HI) derivatives have recently been introduced as potent photoswitches, but their full applicability has hampered by limited possibilities functionalization structural modification. Here we report on a short easy to diversify synthesis yielding diaryl-HIs bearing one additional aromatic residue at central double bond. The resulting chromophores offer an advantageous property profile combining red-light responsiveness, high thermal bistability, strong isomer accumulations both switching directions, photochromism, tunable acid gating. With this progress, broader realm becomes accessible HI which can now be synthetically tailored advanced future applications, e.g., research molecular machines switches, studies photoisomerization mechanisms, or generation smart addressable materials. To showcase potential these distinct light-responsive tools, demonstrate four-state switching, fueling, reversible inscription into transparent polymers using green red light well acid/base stimuli, addition comprehensive photochemical study compounds.

Language: Английский

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Visible‐ and Near‐Infrared Light‐Driven Molecular Photoswitches for Biological Applications

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 19, 2024

Abstract Molecular photoswitches can undergo isomerization under light exposure, making them uniquely attractive for high spatiotemporal resolution remote control of biological functions. Visible and near‐infrared (NIR) light, with their low energy consumption, safety, strong tissue penetration, are particularly suitable applications. Therefore, developing visible‐ NIR light‐driven molecular use is great significance. This review introduces the most common presents state‐of‐art applications in bioimaging, biosensing, drug delivery, photocontrolled cancer phototherapy, photopharmacology. The opportunities challenges future development outlined.

Language: Английский

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Gain of Function Recyclable Photoswitches: Reversible Simultaneous Substitution and Photochromism Generation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: Feb. 7, 2024

Abstract The use of molecular photoswitches has spread to virtually every field pure and applied chemistry because the extraordinary level control they provide over behavior matter at smallest scales. Photoswitches possess least two different states with distinct structures and/or electronics further functionalization their core chromophore is needed tailor them for a specific application. In this work we present concept generation photoswitches. It allows not only simultaneous establishment photochromism functionalization, but also full recyclability non‐photochromic precursor material. Using high‐yielding reversible ammonium salt formation, functional group introduced into symmetric while same time strong electronic push‐pull character established in structure. resulting desymmetrization leads efficient photoswitching capacity can be fully removed subsequently by simple heating step recovering another round. We finally demonstrate feasibility consecutive closed loop functionalization/photoswitching/recovery steps. This offers great potential any chemical research application driven area especially creation responsive reprogrammable materials, no‐background photoswitch labeling, sustainable chemistry.

Language: Английский

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Peri‐Anthracenethioindigo: A Scaffold for Efficient All‐Red‐Light and Near‐Infrared Molecular Photoswitching**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Oct. 9, 2023

Abstract Molecular photoswitching with red light is greatly desired to evade photodamage and achieve specific photoresponses. In virtually all reported cases however, only one switching direction uses while for the reverse switching, UV or visible needed. All‐red‐light brings it clear advantage of pushing limit low‐energy spectrum, but no viable system available currently. Here we report on peri ‐anthracenethioindigo (PAT) as molecular scaffold highly efficient all‐red‐light an outstanding performance property profile. The PAT photoswitch provides near‐infrared (NIR) absorption up 850 nm, large negative photochromism more than 140 nm maxima shifts changes color from green blue upon irradiation two shades light. Thermal stability metastable Z isomer high a corresponding half‐life days at 20 °C. Application in red‐light responsive polymers undergoing pronounced reversible demonstrate spatially resolved photoswitching. thus offers unique responsiveness very low energy together predictable geometrical within rigid scaffold. We expect plethora applications near future, e.g. materials, machines biological context.

Language: Английский

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Getting a molecular grip on the half-lives of iminothioindoxyl photoswitches

Chemical Science, Journal Year: 2024, Volume and Issue: 15(35), P. 14379 - 14389

Published: Jan. 1, 2024

Visible-light-operated photoswitches are of growing interest in reversibly controlling molecular processes, enabling for example the precise spatiotemporal focusing drug activity and manipulating properties materials. Therefore, many research efforts have been spent on seeking control over (photo)physical photoswitches, particular absorption maxima half-life. For photopharmacological applications, should ideally be operated by visible light at least one direction, feature a metastable isomer with half-life 0.1-10 seconds. Here we present our towards engineering iminothioindoxyl (ITI) recently discovered class visible-light-responsive photochromes, whose applicability was hitherto limited half-lives low millisecond range. Through synthesis characterization library ITI variants substantially increased thermal stability, reaching up to 0.2 Based spectroscopic computational analyses, demonstrate how different substituent positions molecule can used tune its photophysical independently fit desired application. Additionally, unique reactivity derivative that featured perfluoro-aromatic ring had most long-lived state shown useful labeling nucleophilic functional groups. The thus paves way using photopharmacology chemical biology.

Language: Английский

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Hemiphosphoindigos as a platform for chiroptical or water soluble photoswitching

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 19, 2025

Abstract Photoswitches are important molecular tools to precisely control the behavior of matter by using light irradiation. They have found application in virtually all applied chemical fields from biology material sciences. However, great challenges remain advanced property design including tailored chiroptical responses or water solubility. Here, hemiphosphoindigo (HPI) photoswitches presented as capable phosphorus-based and a distinct addition established indigoid chromophore family. Phosphinate is embedded core resulting optimized display high thermal stabilities, excellent fatigue resistance isomer enrichment. A series planar, twisted heterocyclic HPIs investigated probe strategies for advantageous photophysical properties. The phosphinate provides platform easily accessible, water-soluble photoswitches, especially interesting biological applications. Its chiral nature further allows light-induced modulation therefore open up structural space photoswitch generation light-responsive

Language: Английский

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Dicyanorhodanine-Pyrrole Conjugates for Visible Light-Driven Quantitative Photoswitching in Solution and the Solid State

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(17), P. 11932 - 11943

Published: April 17, 2024

Small molecule photoswitches capable of toggling between two distinct molecular states in response to light are versatile tools monitor biological processes, control photochemistry, and design smart materials. In this work, six novel dicyanorhodanine-based pyrrole-containing reported. The avails both the

Language: Английский

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Polymer Mechanochemistry of Component Parts for Artificial Molecular Machines

Macromolecular Chemistry and Physics, Journal Year: 2023, Volume and Issue: 224(24)

Published: Oct. 3, 2023

Abstract A huge variety of synthetic molecular machines and their components are developed, actuation at the level is demonstrated used in microscopic systems macroscopic materials. Not only but also mechanical responses critical to applications. In other words, a machine or part insensitive forces can produce work by another external stimulus even under loading as an actuator, whereas that sensitive be controlled generate motions mechanophore. To explore response empirically, it has chemically incorporated polymer chain, through which elongational applied embedded molecule. Here, mechanochemistry component parts reviewed for artificial represented photoswitches mechanically interlocked architectures using mechanochemistry.

Language: Английский

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Photoinduced Multimodal Motions and Reversible Fluorescence Switching in an Elasto‐Plastic Crystal

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: 12(21)

Published: June 17, 2024

Abstract Multi‐stimuli‐responsive materials have received widespread attention in the field of adaptive due to their ability adapt changes environment. However, fabricating multiple stimuli into a single component crystal still remains challenging. In this study, polymorphic elasto‐plastic Schiff‐based displaying morphology‐dependent photomechanical motions is designed and investigated. Both Form I II it exhibit dual plasticity elasto‐plasticity along different facets, which attributed slidable separating layers. Moreover, retains its elastic bending even after being plastically twisted, owing well‐maintained strong π–π interactions, whereas can not twist without fractures. addition, including jumping, twisting are realized by adjusting morphologies, while lacking response ultraviolet light irradiation. Theoretical calculation analysis reveals that lattice deformation induced photoisomerization driving forces for motions. Furthermore, reversible luminescence switching behaviors upon acid‐base fumigation as well heating. The synergistic multi‐stimuli‐responsive mode based on heat, acid, solvent provides an alternative path multi‐mode information encryption.

Language: Английский

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Designing Dynamic Crystals with Multiple Flexibilities through a Cocrystal Strategy for Flexible Photo-controlled Switches

Crystal Growth & Design, Journal Year: 2023, Volume and Issue: 23(12), P. 8637 - 8645

Published: Aug. 16, 2023

Endowing function crystals with flexibility can further extend their applications in the field of flexible smart devices. Herein, a brittle, photo-driven dynamic crystal was successfully modified into through cocrystal strategy. The fluorescence and photo-response properties were simultaneously improved. More importantly, cocrystals exhibit rare multiple flexibilities, including 2D elastic bending twistable deformation properties, which have not been reported before for cocrystals. mechanisms investigated detailed crystallographic analysis, experimental tests, theoretical calculations. It found that be attributed to strong π-stacked columns connecting weak molecular interactions herringbone arrangements are closely related different orientations intermolecular rotation without spatial hindrance. Finally, taking advantage flexibilities cocrystals, photo-controlled switch designed tested.

Language: Английский

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