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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(46), С. 31892 - 31900

Опубликована: Ноя. 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.

Язык: Английский

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Synthesis of Precisely Functionalized Nano-confinement: a Bottom-up Approach to the Evolution of Selective Molecular Receptors

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Precise endo -functionalization tailors the host cavity to fit shape and charge distribution of target guest molecules, offering a novel bottom-up strategy for constructing customized molecular receptors.

Язык: Английский

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

Science China Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 20, 2025

Язык: 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, Год журнала: 2025, Номер 23(10), С. 2498 - 2509

Опубликована: Янв. 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.

Язык: Английский

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Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages

Beilstein Journal of Organic Chemistry, Год журнала: 2025, Номер 21, С. 421 - 443

Опубликована: Фев. 24, 2025

The bespoke environments in enzyme active sites can selectively accelerate chemical reactions by as much 1019. Macromolecular and supramolecular chemists have been inspired to understand mimic these accelerations selectivities for applications catalysis sustainable synthesis. Over the past 60+ years, mimicry strategies evolved with changing interests, understanding, synthetic advances but, ubiquitously, research has focused on use of a molecular "cavity". activities different cavities vary subset features available particular cavity type. Unsurprisingly, without access mimics able encompass more/all functional sites, examples cavity-catalyzed processes demonstrating enzyme-like rate remain rare. This perspective will briefly highlight some key traditional catalysis, type, order contextualize recent development robust organic cage catalysts, which exploit stability, functionality, reduced symmetry enable promising catalytic modes.

Язык: Английский

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Ruthenium(ii) complexes with photoswitchable and photoejectable ligands

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

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

Язык: Английский

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Azobenzene-containing photoresponsive metal-organic cages

Chinese Chemical Letters, Год журнала: 2025, Номер unknown, С. 111135 - 111135

Опубликована: Март 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, Год журнала: 2025, Номер unknown

Опубликована: Март 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.

Язык: Английский

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Light and protonation-controlled complex formation between sulfate and a stiff-stilbene based bis(cyclopeptide)

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A sulfate-binding stiff-stilbene based bis(cyclopeptide) gives rise to 1 : 1, 2 and host–guest assemblies, which can be interconverted by light irradiation acid/base addition.

Язык: Английский

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

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 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.

Язык: Английский

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