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

Maximilian Sacherer,

Sofia Gracheva,

Harald Maid

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 9575 - 9582

Published: March 27, 2024

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

Language: Английский

Design of Collective Motions from Synthetic Molecular Switches, Rotors, and Motors DOI Creative Commons

Damien Dattler,

Gad Fuks, Joakim Heiser

et al.

Chemical Reviews, Journal Year: 2019, Volume and Issue: 120(1), P. 310 - 433

Published: Dec. 23, 2019

Precise control over molecular movement is of fundamental and practical importance in physics, biology, chemistry. At nanoscale, the peculiar functioning principles synthesis individual actuators machines has been subject intense investigations debates past 60 years. In this review, we focus on design collective motions that are achieved by integrating, space time, several or many these mechanical units together. particular, provide an in-depth look at intermolecular couplings used to physically connect a number artificial mechanically active such as photochromic switches, nanomachines based bonds, rotors, light-powered rotary motors. We highlight various can lead their motion length scales. also emphasize how synchronized, desynchronized, behavior emerging functional properties implementation into new devices materials.

Language: Английский

Citations

397

Cyclodextrin‐Based Multistimuli‐Responsive Supramolecular Assemblies and Their Biological Functions DOI

Ying‐Ming Zhang,

Yaohua Liu,

Yu Liu

et al.

Advanced Materials, Journal Year: 2019, Volume and Issue: 32(3)

Published: Feb. 18, 2019

Cyclodextrins (CDs), which are a class of cyclic oligosaccharides extracted from the enzymatic degradation starch, often utilized in molecular recognition and assembly constructs, primarily via host-guest interactions water. In this review, recent progress CD-based supramolecular nanoassemblies that sensitive to chemical, biological, physical stimuli is updated reviewed, intriguing examples biological functions these presented, including pH- redox-responsive drug gene delivery, enzyme-activated specific cargo release, photoswitchable morphological interconversion, microtubular aggregation, cell-cell communication, as well geomagnetism-controlled nanosystem for suppression tumor invasion metastasis. Moreover, future perspectives challenges fabrication intelligent biofunctional materials also discussed at end expected promote translational development nanomaterials biomedical field.

Language: Английский

Citations

350

Loading Photochromic Molecules into a Luminescent Metal–Organic Framework for Information Anticounterfeiting DOI
Zhiqiang Li,

Guannan Wang,

Yingxiang Ye

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(50), P. 18025 - 18031

Published: Oct. 4, 2019

Stimuli-responsive photoluminescent materials have attracted considerable attention owing to their potential applications in security protection because the information recorded directly with static luminescent outputs are usually visible under either ambient or UV light. Herein, we realize reversible anticounterfeiting by loading a photoswitchable diarylethene derivative into lanthanide metal-organic framework (MOF). Light triggers open- and closed-form isomerization of unit, which respectively regulates inactivation activation photochromic FRET process between acceptor donor, resulting luminescence on-off switching emitting center MOF host. This photoresponsive host-guest system allows for multiple pattern visible/invisible transformation simply alternating exposure

Language: Английский

Citations

275

Photoresponsive molecular tools for emerging applications of light in medicine DOI Creative Commons
Ilse M. Welleman, Mark W. H. Hoorens, Ben L. Feringa

et al.

Chemical Science, Journal Year: 2020, Volume and Issue: 11(43), P. 11672 - 11691

Published: Jan. 1, 2020

This perspective article explores the current state of light-controlled molecular tools for medical therapy and imaging offers an outlook on clinical application scenarios optimisation strategies.

Language: Английский

Citations

197

Fluorescent Photochromic α‐Cyanodiarylethene Molecular Switches: An Emerging and Promising Class of Functional Diarylethene DOI
Siyang Lin,

Karla G. Gutierrez‐Cuevas,

Xinfang Zhang

et al.

Advanced Functional Materials, Journal Year: 2020, Volume and Issue: 31(7)

Published: Nov. 3, 2020

Abstract Fluorescent photochromic molecules that exhibit distinct light‐triggered changes in their emission colors are highly desirable for the fabrication of smart soft materials and advanced photonic devices. α‐Cyanodiarylethenes, is, α‐cyano‐functionalized diarylethenes, as alternative “non‐azo” Z/E molecular switches, popular choices due to unique characteristics such aggregation‐induced or aggregation‐induced‐enhanced behavior self‐assembled states, visible fluorescence during photoisomerization. In recent years, development fluorescent α‐cyanodiarylethene‐based compounds including α‐cyanostilbenes, dicyanodistyrylbenzenes, diaryldicyanoethenes, has mainly focused on design, photochemical photophysical solution, matter technologies. this review, significant achievements light‐responsive systems based photoisomerization α‐cyanodiarylethene switches span range from liquid crystals gels finally nanostructures, highlighted. The constructed find use a plethora areas, display, sensing, encrypting, actuating, biomedical imaging applications, among others. review concludes with brief perspective some major challenges opportunities future materials.

Language: Английский

Citations

185

Multi-triggered Supramolecular DNA/Bipyridinium Dithienylethene Hydrogels Driven by Light, Redox, and Chemical Stimuli for Shape-Memory and Self-Healing Applications DOI
Ziyuan Li, Gilad Davidson‐Rozenfeld, Margarita Vázquez‐González

et al.

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(50), P. 17691 - 17701

Published: Nov. 19, 2018

Multi-triggered DNA/bipyridinium dithienylethene (DTE) hybrid carboxymethyl cellulose (CMC)-based hydrogels are introduced. DTE exhibits cyclic and reversible photoisomerization properties, switching between the closed state (DTEc), electron acceptor, open isomer (DTEo) that lacks acceptor properties. One system introduces a dual stimuli-responsive hydrogel containing CMC chains modified with donor dopamine sites self-complementary nucleic acids. In presence of DTEc scaffold, stiff is formed, cooperatively stabilized by dopamine/DTEc donor–acceptor interactions duplex The formation dissociation supramolecular interactions, through light-induced DTE, or via oxidation subsequent reduction sites, leads to switchable stiffness. Another triggered one three alternative signals. stiff, multi-triggered consists cross-linked K+-stabilized G-quadruplexes. G-quadruplexes reversibly separated in 18-crown-6 ether reformed upon addition K+. undergoes transitions high-stiffness low-stiffness states light, redox agents, K+/crown ether. donor–acceptor/G-quadruplex shows shape-memory self-healing features. By using different triggers two memory-codes, e.g., G-quadruplexes, guided function matrices demonstrated.

Language: Английский

Citations

166

Mechanistic Interplay between Light Switching and Guest Binding in Photochromic [Pd2Dithienylethene4] Coordination Cages DOI Creative Commons

Ru-Jin Li,

Julian J. Holstein, Wolf Hiller

et al.

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(5), P. 2097 - 2103

Published: Jan. 8, 2019

Photochromic [Pd2L4] coordination cages based on dithienylethene (DTE) ligands L allow triggering guest uptake and release by irradiation with light of different wavelengths. The process involves four consecutive electrocyclic reactions to convert all chromophores between their open closed photoisomeric forms. So far, affinity the fully switched species was elucidated, but mechanistic details concerning intermediate steps remained elusive. Now, a new member DTE cage family allows unprecedented insight into interplay photoisomerization location inside/outside cavity. Therefore, intrinsic chirality backbones used as reporter for monitoring fate chiral guest. In its "open" form ( o-L, [Pd2( o-L)4] = o-C), C2-symmetric chromophore quickly converts energetically degenerate P M helical conformations. After binding homochiral 1 R-( -) or S-( +) camphor sulfonate R-CSA S-CSA), guest-to-host transfer observed via circular dichroism (CD) signal cage-centered absorption. Irradiating R/S-CSA@ o-C host-guest complexes at 313 nm produced configurationally stable "closed" photoisomers, thus locking induced an enantiomeric excess close 25%. This value (corresponding induction one out ligands), together DOSY NMR, ion mobility mass spectrometry, X-ray structure results, shows that closure first photoswitch is sufficient expel from

Language: Английский

Citations

158

Future‐Oriented Advanced Diarylethene Photoswitches: From Molecular Design to Spontaneous Assembly Systems DOI
Hong‐Bo Cheng, Shuchun Zhang,

En-Ying Bai

et al.

Advanced Materials, Journal Year: 2021, Volume and Issue: 34(16)

Published: Dec. 6, 2021

Diarylethene (DAE) photoswitch is a new and promising family of photochromic molecules has shown superior performance as smart trigger in stimulus-responsive materials. During the past few decades, DAE achieved leap from simple to functional developed toward validity universal switching building block. In recent years, introduction into an assembly system been attractive strategy that enables behavior blocks be manifested at level entire system, beyond unit itself. This assembly-based will bring many unexpected results promote design manufacture generation advanced Here, advances fabrication diarylethene materials science, chemistry, biomedicine are reviewed.

Language: Английский

Citations

131

Stepping Out of the Blue: From Visible to Near‐IR Triggered Photoswitches DOI
Zhiwei Zhang, Wenhui Wang, Michael O’Hagan

et al.

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

Citations

107

Photoswitchable diarylethenes: From molecular structures to biological applications DOI
Ziyong Li,

Xiaoyan Zeng,

Caimin Gao

et al.

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

Published: Sept. 18, 2023

Language: Английский

Citations

76