Solvent‐Free Supramolecular Polymerization for Feather‐Like Nanostructured Chiral Fluorescent Polyurethanes with Multimodal Chiroptical Stimuli Responsiveness

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

Abstract Chiral supramolecular polymers with stimuli‐responsive circularly polarized luminescence (CPL) are highly desirable for smart flexible optoelectronic devices, but remain rarely reported. Here, a simple solvent‐free polymerization preparing chiral polyurethanes is presented by in situ induced self‐assembly strategy, using cellulose nanocrystals (CNCs)‐based isocyanate prepolymers and macromolecular polyols as precursors, achieving precise control over polymer chain assembly spot‐like arrangement. More importantly, further incorporating π‐conjugated luminescent dihydroxynaphthalene molecule, CPL‐active polyurethane films feather‐like nanostructures constructed, which promote the ordered arrangement of CNCs‐based segments due to increased spatial resistance. The π─H bond network between CNCs urethane‐linked benzene rings drives self‐assembly, enabling higher‐level amplification enhanced fluorescence. Interestingly, prepared fluorescent display multimodal chiroptical stimuli responsiveness under various stimuli, such temperature, solvent polarity, pH, light, sensitivity network. This work offers new insights into designing significant potentials.

Язык: Английский

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Dynamic Circularly Polarized Luminescence Switching of Metal–Organic Supramolecular Polymers Directed by the Competition of Solvent-Assisted Nucleation and Thermal Nucleation

Chemistry of Materials, Год журнала: 2024, Номер 36(5), С. 2508 - 2519

Опубликована: Фев. 28, 2024

It is challenging to precisely regulate the chirality transmission of metal–organic supramolecular polymers (MOSPs) due a poor understanding nucleation pathways during highly dynamic and complex self-assembly process. This work reports circularly polarized luminescence (CPL) switching pyridine Schiff-base cholesterol (2-PMPCC) ZnCl2-based MOSPs with inversion CPL through competition solvent-assisted thermal nucleation. In p-xylene, metal 2-PMPCC·ZnCl2 conducted assembled into metastable twisted nanoribbons Agg I right-handed at 490 nm, which further reverted thermodynamic II left-handed nm. contrast, nanosheet-like III 460 nm in ethanol. Based on nucleation, significant morphology were achieved by tuning temperature cosolvents p-xylene revealed transfer transformation regulated solvent-dependent MOSPs, providing an efficient approach control tunable performances for design chiroptical materials.

Язык: Английский

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Supramolecular Chiral J-Aggregates of an Amphiphilic Boron-Azadipyrromethene Dye: Kinetic Pathway and Circularly Polarized Near-Infrared Luminescence

Chemistry of Materials, Год журнала: 2024, Номер 36(8), С. 3745 - 3753

Опубликована: Апрель 4, 2024

An amphiphilic boron-azadipyrromethene (aza-BODIPY) dye (R)-1 bearing two chiral hydrophobic side chains was synthesized, and its supramolecular assembly properties were investigated in detail. The UV/vis absorption, emission, CD spectroscopic studies indicated the pathway complexity aggregation process of (R)-1. In mixed solvent MeOH/H2O, first formed kinetically favored metastable aggregates (Agg. I) upon cooling solution, which could slowly transform into thermodynamically more stable aggregates, i.e., Agg. II by keeping solution I at appropriate temperature. Further kinetic analysis to transformation that an off-pathway aggregate species. displayed distinct spectral morphological characteristics. While a broad absorption band between 656 707 nm observed for I, exhibited extremely narrowed 799 emission 804 J-aggregates. Moreover, AFM TEM revealed spherical nanoparticles had morphology helical nanoribbons. further chiroptical studies, thin film J-aggregated circularly polarized luminescence with maximum g-factor −4.7 × 10–2.

Язык: Английский

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Low-power, non-coherent light-triggered two-photon absorption via extending the lifetime of the transition state

Coordination Chemistry Reviews, Год журнала: 2024, Номер 511, С. 215868 - 215868

Опубликована: Апрель 22, 2024

Язык: Английский

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Reversible Circularly Polarized Luminescence Inversion and Emission Color Switching in Photo-Modulated Supramolecular Polymer for Multi-Modal Information Encryption

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 28, 2024

Constructing circularly polarized luminescence (CPL) materials that exhibit dynamic handedness inversion and emissive color modulation for multimodal information encryption presents both a significant challenge compelling opportunity. Here, we have developed pyridinethiazole acrylonitrile-cholesterol derivative (Z-PTC) exhibits wavelength-dependent photoisomerization photocyclization, enabling in supramolecular assemblies with decent CPL activity. Coordination Ag

Язык: Английский

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Configurationally Stepping Confinement Achieved Tunable Chiral Near‐Infrared Luminescence Supramolecular Phenothiazine Organic Framework

Advanced Science, Год журнала: 2024, Номер 11(42)

Опубликована: Сен. 20, 2024

Herein, thermally responsive reversible chiral supramolecules are reported, constructed by the chirality transfer from tripeptides to achiral network supramolecular organic frameworks (SOF) based on configurationally stepping confinement, which displayed not only highly selective but also efficient enhanced near-infrared (NIR) luminescence. Taking advantage of macrocyclic CB[8] separately encapsulated two kinds tetracationic bis(phenothiazines) derivatives (G1, G2) at 2:1 stoichiometric form 2D SOFs, efficiently enhancing 12.6 fold NIR luminescence and blueshifted 705 680 nm for G1, redshifted 695 710 G2, respectively. Uncommonly, tripeptide coassembled with noncovalent (G1/CB[8] or G2/CB[8]) different opposite circular dichroism signals binding modes affinity, achieving assemblies further fluorescence up 46.2 times quantum yield (QY) increased 0.71% 10.29% G2/CB[8], showing tunable under thermal stimulus. Therefore, current research has achieved controllable SOFs enhancement fluorescence, is successfully applied in logic gates, information encryption, cell imaging.

Язык: Английский

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Photon Upconversion Cooperates with Downshifting in Chiral Systems: Modulation, Amplification, and Applications of Circularly Polarized Luminescence

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(27)

Опубликована: Май 4, 2024

Abstract Circularly polarized luminescence (CPL)‐active materials are increasingly recognized for their potential applications such as 3D imaging, data storage, and optoelectronic devices. Typically, CPL have required high‐energy (HE) photons excitation to emit low‐energy (LE) circularly light, a process known downshifting (DSCPL). However, the emergence of upconverted (UCCPL), where absorption multi LE results in emission single HE photon with circular polarization, has recently attracted considerable attention. This minireview highlights intricate relationship between upconversion phenomena. During upconversion, dissymmetry factor ( g lum ) value can be improved certain systems. Additionally, integration both upconversion‐downshifting‐synergistic systems offers avenues dual‐excitation or dual‐emission functionalities. More detail, emerging UCCPL based on various mechanisms synergy DSCPL introduced. several examples that demonstrate presented highlight future opportunities.

Язык: Английский

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Upconverting and downshifting circularly polarized luminescence in a superstructural helix

Science China Chemistry, Год журнала: 2024, Номер 67(8), С. 2571 - 2577

Опубликована: Июнь 20, 2024

Язык: Английский

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The Effects of Pore Defects in π‐Extended Pentadecabenzo[9]helicene

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(41)

Опубликована: Июль 19, 2024

Abstract The introduction of precise pore defects into nanocarbon structures results in the emergence distinct physicochemical characteristics. However, there is a lack research on non‐planar chiral nanographene involving defects. Herein, we have developed two analogues to π‐extended pentadecabenzo[9]helicene ( EP9H ) containing embedded Each molecules, namely extended dodecabenzo[7]helicene ED7H ; 1 or nonabenzo[5]helicene EN5H 2 ), exhibits dual‐state emission. Significantly, value | g lum exceptionally high at 1.41×10 −2 solution and B CPL as 254 M −1 cm . In PMMA film, 8.56×10 −3 , powder it 5.00×10 This study demonstrates that molecules with exhibit emission properties while maintaining quite good luminescence properties. It was distinguished from aggregation‐caused quenching (ACQ) effect corresponding without defect. Incorporating also simplifies synthesis process enhances solubility resulting product. These findings suggest can be viable approach improve molecules.

Язык: Английский

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Instability-Induced Crystal Self-Assembly in Film-Substrate System for the Construction of Large-Area Micro- and Nano-Chiral Structures

Research Square (Research Square), Год журнала: 2025, Номер unknown

Опубликована: Янв. 9, 2025

Chiral supramolecular self-assembly structures exhibit distinct properties that significantly surpass those of achiral structures, with broad applications in optoelectronics, medicine, biomimetics, and interfaces. However, due to the limited understanding mechanisms underlying generation cross-scale transmission chirality, controlled construction chiral at mesoscopic/macroscopic scales remains a major challenge. Here, we present method based on Instability-Induced Crystal Self-Assembly (IICSA), where external shear triggers instability ibuprofen films, leading transformation from disordered state film large-area, ordered consisting lamellar left-/right-handed fiber combinations via crystallization. Based two-dimensional model, both direct visualization active control dynamics are achieved. The influence surface/interface effects, geometry solid-liquid interactions is revealed through combination theoretical modeling experimental analysis. It has been demonstrated mechanical plays crucial role appearance subsequent evolution structures. Furthermore, application these modulating wettability explored, showing significant impact controlling liquid contact angle. This study not only provides new insights into chirality but also offers novel approach controllable

Язык: Английский

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