Deciphering the mechanism of structural transformation between Pd3L6 and Pd4L8 metal-organic cages

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 20, 2025

Language: Английский

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

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

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Ruthenium(ii) complexes with photoswitchable and photoejectable ligands

Dalton Transactions, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A ruthenium( ii ) complex with a photoswitchable arylazopyrazole ligand is reported.

Language: Английский

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Azobenzene-containing photoresponsive metal-organic cages

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 111135 - 111135

Published: March 1, 2025

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Dissecting the Effects of Cage Structure in the Catalytic Activation of Imide Chlorenium-Ion Donors

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

Published: March 21, 2025

Imide-based chlorinating reagents are mild and easy to use yet can lack the reactivity of charged chlorenium-ion donors. Here, we present a simple strategy for increasing these neutral species by encapsulation inside cationic coordination cage. Using this approach, demonstrate that two different-sized Pd2L4 cages catalyze chlorolactonization chlorocycloetherification reactions acid alcohol functionalized α β-substituted styrene substrates with either 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) or N-chlorosuccinimide (NCS) as chlorenium sources. A kinetic study shows proficient catalysts significant acceleration up 105. However, an unexpected dichotomy is revealed wherein smaller cage, which best preorganized bind nominally provide maximum activation imide reagent, order magnitude less than larger cage has apparently mismatched host–guest chemistry. When scope further extended chlorination simple, unfunctionalized α-methylstyrene, same pattern observed, suggesting differences not explained coencapsulation. Computational studies indicate trend in caused transition state being fixed allowing it find optimal binding thereby generate stronger interactions. This investigation highlights importance understanding underlying mechanisms design new noncovalent greater range transformations.

Language: Английский

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FRET-Mediated Photoswitchable Catalytic Metallacage with Tunable Activity for Organic Dye Degradation

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 2, 2025

Photoswitchable catalysts provide a versatile strategy for controlling catalytic activities through light stimuli, presenting significant potential the precise regulation of synthetic transformations. Herein, we successfully synthesized novel photoswitchable metallacage MC from meso-tetra-(2-pyridyl)-porphines (TPP) and Pt(II)-bisthienylethene (DTE-1) via coordination-driven self-assembly. The ligand within exhibits reversible conversion between its ring-opened ring-closed isomers upon alternating UV visible radiation, facilitating Förster resonance energy transfer (FRET) in systems. Notably, two forms exhibit switchable performance highly poorly catalytical activity degradation Rhodamine B. This work not only develops metallacage-based FRET system but also provides new avenue constructing artificial photoregulated enzymes.

Language: Английский

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Boosting Reaction Kinetics with Viscous Nanowire Dispersions

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

Published: April 22, 2025

Higher viscosity typically slows chemical reactions by restricting molecular movement, while stirring accelerates enhancing reactant diffusion and collisions. However, in this study, we reveal that reaction rates nanowire dispersions─with microscopic ∼300 times of decane, can be enhanced over an order magnitude. Counterintuitively, the with higher causing even greater deceleration. This phenomenon is observed both photo- thermally activated cyclic reactions. Molecular dynamics simulations confocal laser scanning microscopy suggest aliphatic chains grafted onto nanowires interact anisotropic molecules, increasing their local concentrations near nanowires. Notably, azobenzene photoisomerization completely inhibited dispersion, despite completing within 30 s absence We propose align reactive molecules directionally, confined space prevents bulky cis-isomer formation. These findings show not only harvest orient but also exclude products, significantly kinetics systems.

Language: Английский

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

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

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Supramol25: a meeting of the (relatively) new Royal Australian Chemical Institute supramolecular chemistry division

Supramolecular chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 5

Published: April 30, 2025

Language: Английский

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Light, Switch, Action! The Influence of Geometrical Photoisomerization in an Adaptive Self-Assembled System

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

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