Synthesis, Characterization, and Photochemistry of a Ga2L3 Coordination Cage with Dithienylethene-Catecholate Ligands DOI Creative Commons
Adrián Carbonell, Ignacio Izquierdo, David Guzmán

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(42), P. 19872 - 19884

Published: Oct. 8, 2024

Two new photoswitchable dithienylethene (DTE)-catechol ligands, specifically designed for group 13 metal coordination, were synthesized via Suzuki coupling reactions from a dichloro-DTE building block, each with varying longitudinal extensions. The shorter DTE-catechol ligand did not efficiently assemble Ga3+ ions; however, elongation phenylene-amide spacer enabled the successful formation of novel triply DTE-functionalized coordination [Ga2L3]6– cage. This cage represents unique example integrating DTE photoswitches main metals in supramolecular framework. was thoroughly characterized by NMR spectroscopy, including DOSY hydrodynamic volumetric analyses, high-resolution mass spectrometry, computational DFT, and photochemical analyses. DFT studies highlighted structural integrity dynamic interplay within helicate mesocate isomeric forms upon photoswitching. While free ligands exhibited all-photonic reversible switching at up to mM concentrations alternating irradiation 365 >495 nm, demonstrated these capabilities under dilute μM conditions, albeit lower efficiency fatigue resistance. behavior highlights intricate relationship between rigid flexibility

Language: Английский

Photoswitchable Catalysis by a Self-Assembled Molecular Cage DOI Creative Commons
Ray G. DiNardi, Samina Rasheed, Simona S. Capomolla

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21196 - 21202

Published: July 25, 2024

A heteroleptic [Pd

Language: Английский

Citations

22
Photoswitchable Imines Drive Dynamic Covalent Systems to Nonequilibrium Steady States DOI Creative Commons
Jiarong Wu, Jake L. Greenfield

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 20720 - 20727

Published: July 18, 2024

Coupling a photochemical reaction to thermal exchange process can drive the latter nonequilibrium steady state (NESS) under photoirradiation. Typically, systems use separate motifs for photoresponse and equilibrium-related processes. Here, we show that photoswitchable imines fulfill both roles simultaneously, autonomously driving dynamic covalent system into NESS continuous light irradiation. We demonstrate this using transimination reactions, where

Language: Английский

Citations

12
Thiosemicarbazones as versatile photoswitches with light-controllable supramolecular activity DOI Creative Commons

Bengi Sentürk,

Burkhard Butschke, Fabian Eisenreich

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Using photoswitchable molecules to manipulate supramolecular interactions under light illumination has driven advancements in numerous fields, allowing for the strategic alteration of molecular systems. However, integrating moiety responsible these into photochromic scaffold can be complex and may hamper switching efficiency. We thus explored a simple class organic molecules, namely thiosemicarbazones, featuring both photoisomerizable C[double bond, length as m-dash]N double bond thiourea capable hydrogen bonding. The scalable two-step synthesis allowed us prepare 23 thiosemicarbazones systematically elucidate their optical properties. Attaching various functional groups, extended π-systems, heterocycles enabled fine-tuning absorption profiles. UV converts from stable E-isomer metastable Z-isomer, exhibiting negative positive T-type photochromism, wide range thermal half-lives, PSS values up 92%, high fatigue resistance. Substituting with pyridinyl group stabilizes Z-isomer via intramolecular bonding, confirmed by single-crystal X-ray analysis, transforms bistable P-type photoswitches. Additionally, dimerize or form aggregates through bonding-a process that turned off on light. Overall, offer tunable properties, rendering them promising photoswitch creating stimuli-responsive

Language: Английский

Citations

0
Precise Assembly/Disassembly of Homo-Type and Hetero-Type Macrocycles with Photoresponsive and Non-Photoresponsive Dynamic Covalent Bonds DOI

Junmiao Deng,

Hanwei Lu, Hebo Ye

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: 23(10), P. 2498 - 2509

Published: Jan. 1, 2025

Dynamic covalent macrocycles offer the advantage of tunable ring-opening/ring-closure and structural transformation, but their control with precision remains a daunting task due to labile nature reversible bonds. Herein we demonstrate precise formation/scission varied sizes by contrasting reactivity, stability, degradability light-active light-inactive dynamic The incorporation photoswitchable non-photoresponsive aldehyde sites into one single dialdehyde component afforded creation [1 + 1] type primary diamines suitable lengths. manipulation light acid/base stimuli allowed on-demand breaking/remaking macrocycles, achieving interconversion between macrocyclic linear skeletons. Moreover, combination dialdehyde, diamines, secondary enabled construction hetero-type [2 1 1'] via enhanced discrimination hierarchical assembly. Light-induced kinetic locking/unlocking bonds further macrocycle-to-macrocycle conversion when needed. Through leveraging controllable connection/disconnection, switchable formation/disintegration mechanically interlocked catenanes was accomplished. results described showcase potential photoinduced chemistry for preparing complex architectures should set stage molecular recognition, assemblies, synthetic motors, responsive materials.

Language: Английский

Citations

0
Manipulating the Isomerization of a Tris-azobenzene Cage by Anion Binding DOI

Hongqing Shan,

Wei Zhao, Ji Wang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Here, we report a C3-symmetric tris-azobenzene cage 1 comprising azobenzene cores and bis(urea) units. This system demonstrates efficient reversible photoisomerization unprecedented anion-mediated switching modes. Specifically, the phosphate anion induces concerted ZZZ → EEE isomerization with prolonged thermal relaxation (t1/2 = 37.5 h at 298 K). In contrast, bulky benzene-1,3,5-tricarboxylate enforces stepwise pathway (ZZZ EZZ EEZ EEE) rapid 54.4, 44.5, 12.9 min for each step). study represents first demonstration of selective control over multi-azobenzene switch, mimicking biological adaptability through environmental changes.

Language: Английский

Citations

0
Multiple control of azoquinoline based molecular photoswitches DOI Creative Commons

Youming Lv,

Hebo Ye, Lei You

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(9), P. 3290 - 3299

Published: Jan. 1, 2024

Multi-addressable molecular switches with high sophistication are creating intensive interest, but challenging to control. Herein, we incorporated ring-chain dynamic covalent sites into azoquinoline scaffolds for the construction of multi-responsive and multi-state switching systems. The manipulation equilibrium by acid/base reactions primary/secondary amines allowed regulation E/Z photoisomerization. Moreover, carboxyl quinoline motifs provided recognition handles chelation metal ions turning off photoswitching, otherwise inaccessible Z-isomer complexes obtained via change stimulation sequence. Particularly, distinct binding behaviors primary amine secondary products offered a facile way modulating reactivity. As result, multiple control azoarene photoswitches was accomplished, including light, pH, ions, nucleophiles, interplay between diverse stimuli further enabling addressable within reaction networks. underlying structural mechanistic insights were elucidated, paving creation complex systems, assemblies, intelligent materials.

Language: Английский

Citations

3
Light, Switch, Action! The Influence of Geometrical Photoisomerization in an Adaptive Self-Assembled System DOI Creative Commons
Marco Ovalle, Charlotte N. Stindt, Ben L. Feringa

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(46), P. 31892 - 31900

Published: Nov. 5, 2024

The ubiquitous ability of natural dynamic nanostructures to adapt environmental changes is a highly desirable property for chemical systems, particularly in the development complex matter, molecular machines, and life-like materials. Designing such systems challenging due generation mixtures with responses that are difficult predict, characterize, diversify. Here, we navigate between self-assembled architectures using light by operating an intrinsic photoswitchable building block governs state system. When complementary units present, photoswitch determines predominant architecture, reversibly adapting cage macrocycles, including (otherwise inaccessible) higher-energy assemblies. Our study showcases this concept seven different transformations, offering unprecedented degree control, diversification, adaptation self-selecting units. These findings could enable applications on-demand dissipative macrocycles based on bonds. We also envision transient nanostructures, e.g., reticular polymeric materials, being explored fine-tuning nature unit.

Language: Английский

Citations

3
Host‐Guest Stimuli‐Responsive Click Chemistry DOI Creative Commons
Arturo Blanco‐Gómez, Mauro Díaz‐Abellás, Iván Montes de

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(33)

Published: April 10, 2024

Click chemistry has reached its maturity as the weapon of choice for irreversible ligation molecular fragments, with over 20 years research resulting in development or improvement highly efficient kinetically controlled conjugation reactions. Nevertheless, traditional click reactions can be disadvantageous not only terms efficiency (side products, slow kinetics, air/water tolerance, etc.), but also because they completely avoid possibility to reversibly produce and control bound/unbound states. Recently, non-covalent appeared a more alternative, particular by using host-guest self-assembled systems high thermodynamic stability kinetic lability. This review discusses implementation switches such processes, what we have termed stimuli-responsive chemistry, which constitutional states system favored external stimulation, complexes. As exemplify handpicked selected examples, these supramolecular are well suited human-controlled conjugation, coupling thermodynamically regulated processes appropriate temporally resolved extrinsic mechanisms, thus mimicking nature advancing our efforts develop function-oriented chemical synthesis.

Language: Английский

Citations

2
Photoswitchable catalysis by a self-assembled molecular cage DOI Creative Commons
Ray G. DiNardi, Samina Rasheed, Simona S. Capomolla

et al.

Published: June 25, 2024

A heteroleptic [Pd2L2L'2]4+ coordination cage containing a photoswitchable azobenzene-derived ligand catalyzes the Michael addition reaction between methyl vinyl ketone and benzoyl nitromethane within its cavity. The correspond-ing homoleptic cages are catalytically inactive. can be reversibly disassembled reassembled using 530 nm light 405 light, respectively, allowing catalysis to switched ON OFF at will.

Language: Английский

Citations

1
Light‐Responsive Aldehyde‐Reduction Catalysis Through Catalyst Encapsulation DOI Creative Commons
Jonathan R. Nitschke, Amit Ghosh, John D. Thoburn

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

Abstract We report a light‐responsive tetrahedral metal–organic capsule that binds perrhenate catalyst, which is released selectively upon irradiation with 350 nm light, turning on the catalytic reduction of organic carbonyls by hydrosilanes. The activity can be switched off heating at 75 °C for 2.5 h, stimulates reformation and catalyst re‐encapsulation. Multiple on‐off cycles were shown, clear relationship between product yield light time. Encapsulation thus enables coupling light‐responsiveness to catalysis in manner might generalized other catalysts capsules.

Language: Английский

Citations

0