Photoresponsive Supramolecular Polymers: From Light‐Controlled Small Molecules to Smart Materials

Advanced Materials, Journal Year: 2022, Volume and Issue: 35(10)

Published: Oct. 14, 2022

Photoresponsive supramolecular polymers are well-organized assemblies based on highly oriented and reversible noncovalent interactions containing photosensitive molecules as (co-)monomers. They have attracted increasing interest in smart materials dynamic systems with precisely controllable functions, such light-driven soft actuators, photoresponsive fluorescent anticounterfeiting light-triggered electronic devices. The present review discusses light-activated used their main photo-induced changes, e.g., geometry, dipole moment, chirality. Based these distinct formed by exhibit disassembly reassembly. As a consequence, polymerization, "depolymerization," regulation of the lengths topologies observed. Moreover, light-controlled functions polymers, actuation, emission, chirality transfer along length scales, highlighted. Furthermore, perspective challenges future opportunities is presented. Besides challenge moving from harmful UV light to visible/near IR avoiding fatigue, enabling biomedical applications, include actuators helical motion, light-modulated information transmission, optically recyclable materials, multi-stimuli-responsive systems.

Language: Английский

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Stepping Out of the Blue: From Visible to Near‐IR Triggered Photoswitches

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(31)

Published: May 7, 2022

Abstract Light offers unique opportunities for controlling the activity of materials and biosystems with high spatiotemporal resolution. Molecular photoswitches are chromophores that undergo reversible isomerization between different states upon irradiation light, allowing a convenient means to control their influence over system interest. However, significant limitation classical is requirement initiate switching in one or both directions using deleterious UV light poor tissue penetration. Red‐shifted hence demand have attracted keen recent research In this Review, we highlight progress towards development visible‐ NIR‐activated characterized by distinct photochromic reaction mechanisms. We hope inspire further endeavors field, full potential these tools biotechnology chemistry applications be realized.

Language: Английский

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Rational Design in Photopharmacology with Molecular Photoswitches

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: April 7, 2023

Photopharmacology is an attractive approach for achieving targeted drug action with the use of light. In photopharmacology, molecular photoswitches are introduced into structure biologically active small molecules to allow optical control their potency. Going beyond trial and error, photopharmacology has progressively applied rational design methodologies devise light-controlled bioactive ligands. this review, we categorize photopharmacological efforts from standpoint medicinal chemistry strategies, focusing on diffusible photochromic ligands modified that operate through E-Z bond isomerization. vast majority cases, photoswitchable designed as analogs existing compounds, a variety approaches. By analyzing in detail comprehensive list instructive examples, describe state art discuss future opportunities photopharmacology.

Language: Английский

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Smart Photochromic Materials Triggered with Visible Light

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(19)

Published: Feb. 26, 2022

Abstract Molecular photoswitches reversibly convert the energy of light into a variety structural changes at molecular level. They can be integrated smart materials with broad range applicability. While most photochromic systems require UV for activation, application operational entirely within visible or NIR brings considerable benefits, such as biocompatibility, better penetration through material, propelling sunlight, possibility to design dual that are mutually activated frequencies two distinct functions. In this Review, we discuss relevant classes photoswitches, and demonstrate selection polymers, gels, porous materials, surfaces, energy‐storing other triggered light.

Language: Английский

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A Dihydroazulene‐Based Photofluorochromic AIE System for Rewritable 4D Information Encryption

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(37)

Published: July 16, 2022

Dynamic patterns based on luminescent materials play an essential role in the digital age. However, it is still challenging to develop highly emissive photofluorochromic with dynamic behaviors store information multiple characteristics. Here, we report a series of dihydroazulene-based compounds which show typical aggregation-induced emission (AIE) effect. Moreover, photo-switching ability dihydroazulene units, undergoing light-induced ring-opening, enables properties. The photofluorochromism also shows quantitively described responses time and temperature via reverse ring-closing process. Ultimately, rewritable 4D system, embedded quick response code, dot matrix microstructures, color fluorescence, time/temperature-dependent intensity change, established patterns. This work not only develops AIE skeleton properties but provides new strategy for encryption cybernetics.

Language: Английский

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Photoswitchable diarylethenes: From molecular structures to biological applications

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 497, P. 215451 - 215451

Published: Sept. 18, 2023

Language: Английский

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Metal–Photoswitch Friendship: From Photochromic Complexes to Functional Materials

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(51), P. 23249 - 23263

Published: Dec. 13, 2022

Cooperative metal–photoswitch interfaces comprise an application-driven field which is based on strategic coupling of metal cations and organic photochromic molecules to advance the behavior both components, resulting in dynamic molecular material properties controlled through external stimuli. In this Perspective, we highlight ways interplay can be utilized as a tool modulate system's physicochemical performance variety structural motifs, including discrete complexes or cages, well periodic structures such metal–organic frameworks. This Perspective starts with smallest subunit interactions occur, progresses toward functional materials. particular, explore role relationship for gaining fundamental knowledge switchable electronic magnetic properties, design stimuli-responsive sensors, optically gated memory devices, catalysts, photodynamic therapeutic agents. The abundance systems natural world only foreshadows creative directions that will uncover full potential coming years.

Language: Английский

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Photoswitchable coordination cages

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(1), P. 13 - 21

Published: Jan. 1, 2024

Language: Английский

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Phenylazothiazoles as Visible-Light Photoswitches

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 9072 - 9080

Published: April 12, 2023

A novel class of photoswitches based on a phenylazothiazole scaffold that undergoes reversible isomerization under visible-light irradiation is reported. The photoswitch, which comprises thiazole heteroaryl segment directly connected to phenyl azo chromophore, has very different spectral characteristics, such as redshifted absorption maximum wavelength and well-separated bands the trans cis isomers, than conventional azobenzene other compounds. Substituents at ortho para positions ring photoswitch resulted in further shift longer wavelengths up 525 nm with small thermal stability compensation. These showed excellent photostationary distributions half-lives 7.2 h, reductant stability. X-ray crystal structure analysis revealed isomers exhibited planar geometry T-shaped orthogonal geometry. Detailed ab initio calculations demonstrated plausible electronic transitions energy barriers, were consistent experimental observations. fundamental design principles elucidated this study will aid development wide variety for photopharmacological applications.

Language: Английский

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Ultra-photostable small-molecule dyes facilitate near-infrared biophotonics

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 22, 2024

Abstract Long-wavelength, near-infrared small-molecule dyes are attractive in biophotonics. Conventionally, they rely on expanded aromatic structures for redshift, which comes at the cost of application performance such as photostability, cell permeability, and functionality. Here, we report a ground-state antiaromatic strategy showcase concise synthesis 14 cationic aminofluorene with mini (molecular weights: 299–504 Da) distinct spectra covering 700–1600 nm. Aminofluorene cell-permeable achieve rapid renal clearance via simple 44 Da carboxylation. This accelerates optical diagnostics injury by 50 min compared to existing macromolecular approaches. We develop compact molecular sensing platform vivo intracellular sensing, demonstrate versatile applications these multispectral fluorescence optoacoustic imaging. find that aromaticity reversal upon electronic excitation, indicated magnetic descriptors, not only reduces energy bandgap but also induces strong vibronic coupling, resulting ultrafast excited-state dynamics unparalleled photostability. These results support argument antiaromaticity useful design rule dye development, enabling performances essential modern

Language: Английский

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