Engineering Helical Chirality in Metal-Coordinated Cyclodextrin Nanochannels

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 7325 - 7335

Опубликована: Фев. 18, 2025

Helicates are a defining element of DNAs and proteins, with functions that critical to variety biological processes. Cyclodextrins promising candidates for forging multiple-stranded helicates well-defined helicity, but lack available tools has precluded the construction artificial helical nanochannels controllable geometry helicity from these widely chiral building blocks. Herein, we disclose family Ag6L2 can be readily assembled α-cyclodextrin-derived ligands through coordination between pyridinyl groups Ag+ cations. We discovered exhibit either an M or P when cations adopt tetrahedral while losing most their linearly coordinated. Both precisely controlled by simply changing number methyl at ortho positions ligands. The tetracoordinated interconnect into infinite two-dimensional coordinative network characterized hexagonal tessellation. Theoretical calculations, which reveal lower energies conformations observed in crystals compared those inverted counterparts, support experimental results.

Язык: Английский

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Host–Guest Interactions Induced Enhancement in Oxidase-Like Activity of a Benzothiadiazole Dye Inside an Aqueous Pd₈L₄ Barrel

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(36), С. 24901 - 24910

Опубликована: Авг. 28, 2024

The effect of host–guest interactions on the chemistry encapsulated molecules is a fascinating field research that has gained momentum in recent years. Much work this been focused such catalysis and photoluminescence dyes. However, related photoinduced processes, as photoregulated oxidase-mimicking activity, not explored much. Herein, we report unique example enhancement oxidase-like activity benzothiadiazole dye (G1) water through encapsulation within M8L4 molecular barrel (1). Favorable helped guest G1 to have better electron transfer oxygen leading increased production superoxide radical anions activity. Furthermore, inside 1 also caused change redox potentials which after produced oxidizing agent than free G1. These phenomena combined enhance upon cage 1. present demonstrates processes.

Язык: Английский

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Boosting the circularly polarized luminescence of pyrene-tiaraed pillararenes through mechanically locking

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Дек. 3, 2024

Attributed to their unique dynamic planar chirality, pillar[n]arenes, particularly pillar[5]arenes, have evolved as promising platforms for diverse applications such circularly polarized luminescence (CPL) emitters. However, due the unit flipping and swing, achievement of excellent CPL performances pillar[5]arenes in solution state remains a formidable challenge. To deal with this key issue, mechanically locking approach has been successfully developed, leading boosted dissymmetry factor (glum) values pyrene-tiaraed up 0.015 through formation corresponding [2]rotaxanes. More importantly, taking advantage stably locked co-conformers, these resultant [2]rotaxanes maintain solvents wide range concentrations, making them candidates practical applications. According proof-of-concept study, we not only developed powerful strategy rational design chiral luminescent materials desired but also contributed platform construction smart materials. Due pillar[n]arenes are emitters efficient emission is challenge swing. Here, authors report

Язык: Английский

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Optical Axial Chirality Enhancement and Transfer within Aromatic Micelles upon (Co-)encapsulation

JACS Au, Год журнала: 2025, Номер 5(2), С. 586 - 592

Опубликована: Фев. 3, 2025

Axial chirality is the key physiochemical element, yet its chiroptical utilities have been largely limited to covalent synthesis and infinitely assembled systems so far. Here we report a new application of axially chiral binaphthyls for efficient, optical enhancement transfer upon noncovalent encapsulation by achiral aromatic micelles in water. The CD activities dialkoxy are significantly enhanced (up 7-fold) an anthracene-based micelle. Large emission (∼4-fold) efficient guest-to-guest, achieved through coencapsulation with cycloparaphenylenes, guest-within-guest fashion, observed unusual properties derived from tight inclusion guests into macrocyclic guests, efficiently generated only cavity. Moderate CPL can be coencapsulated macrocycles within ternary composites. Furthermore, more than ∼4-fold guest-to-guest demonstrated functionalized cycloparaphenylene present strategy.

Язык: Английский

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Chiral Porous Frameworks for Enantioselective Separation and Asymmetric Catalysis

Chinese Journal of Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 19, 2025

Comprehensive Summary The preparation and resolution of chiral molecules hold significant importance in scientific industrial domains, such as drug development manufacturing. In recent years, porous frameworks have attracted increasing attention asymmetric catalysis enantiomer due to their excellent performance. metal‐organic (MOFs), covalent organic (COFs), cages (POCs), coordination (PCCs) are important representative the framework family. Significantly, chirality can be easily introduced into these materials through simple bottom‐up or post‐modification methods, thereby promoting applications related chirality. this review, we systematically summarize synthesis strategies four classes enantiomeric resolution. Finally, present some perspectives on future frameworks. Key Scientists Significant progress has been made frameworks, primarily driven by application molecules. This area research seen contributions from many distinguished scientists. A particularly milestone was reached 2000, when Kimoon Kim reported first catalytic Chiral Metal‐Organic Framework (CMOF). 2001, Lin et al . a new generation recyclable CMOF capable separation heterogeneous catalysis. Simultaneously, researchers Cui Duan substantial contributions, advancing field considerably. Furthermore, notable developments Covalent Organic Frameworks (CCOFs), with pioneering work like Jiang, Wang, Cui. Meanwhile, groups Su Li strides cages. These remarkable accomplishments drawn considerable interest.

Язык: Английский

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Dynamic Chirality in Nature-Inspired Photonic Crystal Films: Ultralong Room Temperature Phosphorescence and Stimuli-Responsive Circularly Polarized Luminescence

ACS Nano, Год журнала: 2025, Номер unknown

Опубликована: Март 11, 2025

Circularly polarized luminescence (CPL) systems exhibiting room-temperature phosphorescence (RTP) are attracting considerable attention for applications in information encryption and smart sensing. However, achieving ultralong circularly RTP (CPRTP) with tunable chirality stimuli-responsive CPL remains challenging. Inspired by the color-changing properties of Troides magellanus butterfly, we developed a cellulose nanocrystal (CNC)-based photonic crystal film an lifetime 2.04 s. The helical pitch could be engineered adding different amounts glucose, leading to 3-fold 4-fold enhancement fluorescence quantum yields, respectively, compared samples without glucose. system exhibited green afterglows lasting over 4 s bandgap (PBG) that modulated chiroptical properties, high glum values −0.749 −0.650 phosphorescence. Additionally, demonstrated features such as humidity-responsive solvent-responsive CPL. Therefore, biomimetic offers promising opportunities multilevel anticounterfeiting, security, sensing applications.

Язык: Английский

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Chiral covalent organic cages: Construction and chiral functions

Smart Molecules, Год журнала: 2025, Номер unknown

Опубликована: Март 25, 2025

Abstract Covalent organic cages (COCs) are three‐dimensional molecules with permanent cavities, known for their ordered pore structures, excellent processability, and modular design. They have shown significant potential in applications such as gas adsorption, molecular separation, catalysis. Introducing chiral elements into COCs results confined which endows them unique functions expands application prospects. This review summarizes the research progress on covalent cages, focusing strategies incorporating elements, structures synthesis methods of representative COCs, advancements functions. Additionally, we provide perspectives future directions. We hope this will inspire further interest creativity among researchers field leading to development materials

Язык: Английский

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Chiral Amplification and Regulation: Design and Applications of Circularly Polarized Luminescence‐Active Materials Derived From Macrocyclic Compounds

Aggregate, Год журнала: 2025, Номер unknown

Опубликована: Май 9, 2025

ABSTRACT Chirality is a fundamental property in molecules and biological systems, characterized by asymmetric configurational features. Circularly polarized luminescence (CPL) materials have gained significant attention due to their unique optical activities, with applications 3D displays, chiral sensors, catalysis, more. Chiral transfer amplification typically involve the generation of chirality excited state, facilitated interactions like energy transfer, electron or induction. Supramolecular self‐assembly strategies, particularly macrocyclic compounds, enable linking achiral luminescent units through intermolecular interactions. Macrocyclic hosts—cyclodextrins, calix[ n ]arenes, pillar[ cyclophanes, cucurbit[ ]urils—are especially promising stable structures adjustable cavities for guest encapsulation. These compounds induce photophysical properties host–guest complexation, making them ideal constructing amplification, CPL‐active materials. This review summarizes advancements multicolor CPL materials, sensing, induction, separation, highlighting potential supramolecular material design. The challenges future directions this field are also discussed, aiming guide further research application systems.

Язык: Английский

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Hierarchical Chiral Luminescent Macrocyclic Porous Organic Polymer from Chiral π-Conjugated Macrocycles: Tunable Circularly Polarized Luminescence and Enantiomeric Fluorescent Sensing

Macromolecules, Год журнала: 2025, Номер unknown

Опубликована: Июнь 3, 2025

Язык: Английский

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Catalytic Enantioselective Synthesis of Planar Chiral Pillar[5]arenes via Asymmetric Sonogashira Coupling

Опубликована: Июнь 12, 2024

As a novel type of macrocycles with attractive planar chirality, pillar[5]arenes have gained increasing research interest over the past decades, enabling their widespread applications in diverse fields such as porous materials, molecular machines, and chiral luminescence materials. However, catalytic methodology towards enantioselective synthesis remains elusive. Here we report method for via asymmetric Sonogashira coupling, giving access to wide range highly functionalized pillar[5]arenes, including both homo- hetero-rimmed ones, excellent enantioselectivities. Attractively, resultant show great potential use many areas luminescent This work not only enables successful abundant structural functional diversity key building blocks practical but also enriches cross-coupling methodologies organic synthetic chemistry.

Язык: Английский

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