Aggregation and luminescence in carbonized polymer dots

Aggregate, Journal Year: 2022, Volume and Issue: 3(2)

Published: Jan. 20, 2022

Abstract The aggregate luminescence behavior of organic luminescent materials has been studied extensively. As a new kind nanomaterials, carbonized polymer dots (CPDs) not only inherit the stability and biocompatibility carbon materials, but also possess tunability, water solubility, high photoluminescence quantum yield rendering them strong candidate for next generation light‐emitting materials. Previously, people mainly understood its from perspective some mechanisms are still unclear. In this review, we discuss mechanism by referring to with emphasis on their aggregation behavior. Firstly, three representative phenomena briefly introduced. Chromophores present in CPDs elaborated further potential interactions between them, role crosslinked networks. On basis, special state summarized, relevant discussed detail consolidate statements.

Language: Английский

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Aliphatic Polyesters with White-Light Clusteroluminescence

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(33), P. 15286 - 15294

Published: July 7, 2022

Single-molecule white-light emission (SMWLE) has many advantages in practical applications; however, the fabrication of SMWLE from nonconjugated luminescent polymers, namely, clusteroluminogens (CLgens), is still a big challenge. Herein, first example linear polyesters with reported. Twenty-four kinds aliphatic tunable clusteroluminescence (CL) colors and efficiency were synthesized by copolymerization six epoxides four anhydrides. Experimental calculation results prove that, at primary structure level, balance structural flexibility rigidity via adjusting side-chain length significantly enhances CL without wavelength change. However, altering chemical structures monomer succinic anhydride to trans-maleic (MA), cis-MA, citraconic (CA), secondary these change helix straight folding sheet accompanied gradually red-shifted 460 570 nm due increase through-space n–π* interactions, as demonstrated computational experimental results. Then, pure CIE coordination (0.30, 0.32) based on overlapped short-wavelength long-wavelength achieved CA-based polyesters. This work not only provides further insights into mechanism but also new strategy manipulate properties regulating hierarchical CLgens.

Language: Английский

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Hyperbranched Polyborate: A Non‐conjugated Fluorescent Polymer with Unanticipated High Quantum Yield and Multicolor Emission

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(29)

Published: May 2, 2022

Abstract Non‐conjugated fluorescent polymers have attracted great attention due to their excellent biocompatibility and environmental friendliness. However, it remains a huge challenge obtain polymer with high fluorescence quantum yield (QY) multicolor emission simultaneously. Herein, we reported three kinds of nonaromatic hyperbranched polyborates ( P1 – P3 ) emission, surprisingly, P2 also exhibits an unanticipated QY (54.1 %). The natural bond orbital (NBO) analysis density functional theory (DFT) calculation results revealed that the synergistic effect rigid BO 3 planar flexible carbon chain, as well through‐space dative in supramolecular aggregate, were key factors contributing ultrahigh . Moreover, applications Fe 3+ ions detection cell imaging investigated. This work provides new perspective for designing non‐conjugated both emission.

Language: Английский

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Secondary through-space interactions facilitated single-molecule white-light emission from clusteroluminogens

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 17, 2022

Clusteroluminogens refer to some non-conjugated molecules that show visible light and unique electronic properties with through-space interactions due the formation of aggregates. Although mature systematic theories molecular photophysics have been developed study conventional conjugated chromophores, it is still challenging endow clusteroluminogens designed photophysical by manipulating interactions. Herein, three donor-acceptor structures different halide substituents are synthesized. These compounds multiple emissions even single-molecule white-light emission in crystalline state. The intensity ratio these easily manipulated changing atom excitation wavelength. Experimental theoretical results successfully disclose nature emissions: conjugation for short-wavelength fluorescence, charge transfer based on secondary long-wavelength room-temperature phosphorescence. introduction not only enriches their varieties but also inspires establishment novel aggregate clusteroluminescence.

Language: Английский

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Manipulation of clusteroluminescence in carbonyl‐based aliphatic polymers

Aggregate, Journal Year: 2022, Volume and Issue: 3(6)

Published: Oct. 14, 2022

Abstract Clusteroluminogens (CLgens), nonconjugated structures with visible luminescence at the clustering state, have recently received remarkable attention due to their great theoretical significance and practical values. In carbonyl‐based aliphatic polymers, ( n , π *) transition of carbonyl groups through‐space interactions been demonstrated play an important role in clusteroluminescence (CL) properties, but it is still a big challenge manipulate CL molecular level. this work, six polymers different heteroatoms steric hindrances were synthesized, photophysical properties systematically studied. These all showed emission efficiency wavelength. Experimental studies indicated that could be manipulated by changing electronic rigidity polymer chains. This work not only gains further insights into mechanism also provides reliable strategies design non‐conjugated luminescent materials.

Language: Английский

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Anionic polymerization of nonaromatic maleimide to achieve full-color nonconventional luminescence

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 28, 2022

Nonconventional or nonconjugated luminophore without polycyclic aromatics extended π-conjugation is a rising star in the area of luminescent materials. However, continuously tuning emission color within broad visible region via rational molecular design remains quite challenging because mechanism nonconventional luminescence not fully understood. Herein, we present new class luminophores, poly(maleimide)s (PMs), with full-color that can be finely regulated by anionic polymerization even at ambient temperature. Interestingly, general characteristics luminescence, cluster-triggered emission, e.g., concentration-enhanced are observed PMs. Instead, PMs have features similar to aggregation-caused quenching due boosted intra/inter-molecular charge transfer. Such biocompatible material synthesized from low-cost monomer shows great prospects large-scale production and applications, including security printing, fingerprint identification, metal ion recognition, etc. It also provides platform achieve any aromatics.

Language: Английский

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Molecular-level enhanced clusterization-triggered emission of nonconventional luminophores in dilute aqueous solution

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Jan. 25, 2023

Abstract Nonconjugated and nonaromatic luminophores based on clustering-triggered emission derived from through-space conjugation have drawn emerging attention in recent years. The reported nonconventional are emissive concentrated solution and/or the solid state, but they tend to be nonluminescent dilute solution, which greatly limits their sensing imaging applications. Herein, we design unique clusteroluminogens through modification of cyclodextrin (CD) with amino acids enable intermolecular intramolecular clusterization chromophores CD-based confined space. resulted interactions along conformation rigidification originated hydrogen bond interaction complexation generate blue cyan fluorescence even (0.035 wt.%, quantum yield 40.70%). Moreover, prepared histidine-modified CD (CDHis) is demonstrated for fluorescent detection chlortetracycline high sensitivity selectivity. This work provides a new universal strategy synthesize bright aqueous molecular-level enhanced clusterization-triggered emission.

Language: Английский

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Hyperbranched Polyborosiloxanes: Non‐traditional Luminescent Polymers with Red Delayed Fluorescence

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(48)

Published: Sept. 27, 2023

Non-traditional fluorescent polymers have attracted significant attention for their excellent biocompatibility and diverse applications. However, designing preparing non-traditional that simultaneously possess long emission wavelengths fluorescence lifetime remains challenging. In this study, a series of novel hyperbranched polyborosiloxanes (P1-P4) were synthesized. As the electron density increases on monomer diol, optimal P1-P4 gradually red-shift to 510, 570, 575, 640 nm, respectively. particular, P4 not only exhibits red but also demonstrates delayed with 9.73 μs lowest critical cluster concentration (1.76 mg/mL). The experimental results theoretical calculations revealed synergistic effect dual heteroatom-induced delocalization through-space O⋅⋅⋅O O⋅⋅⋅N interaction was key factor contributing red-light fluorescence. Additionally, these showed potential in dual-information encryption. This study provides universal design strategy development unconventional both long-wavelength emission.

Language: Английский

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Enabling nonconjugated polyesters emit full-spectrum fluorescence from blue to near-infrared

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 8, 2024

Abstract Near-infrared luminophores have many advantages in advanced applications, especially for structures without π-conjugation aromatic rings. However, the fabrication of red clusteroluminogens from nonconjugated polymers is still a big challenge, let alone near-infrared clusteroluminogens. Here, we develop with full-spectrum blue to light (470 ~ 780 nm), based on color phenomenon polyesters synthesized amine-initiated copolymerization epoxides and cyclic anhydrides. We reveal that amines act as initiators attached polymer chain ends. The formation various amine-ester complexes induces light, conceptually, complexed clusteroluminescence via intra/inter-chain charge transfer. Significantly, emission colors can be easily tuned by contents types amines, microstructures polyesters, their concentration. This work provides low-cost, scalable platform strategy production high-efficiency, multicolor luminescent materials.

Language: Английский

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Cluster‐Triggered Self‐Luminescence, Rapid Self‐Healing, and Adaptive Reprogramming Liquid Crystal Elastomers Enabled by Dynamic Imine Bond

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(31)

Published: April 17, 2024

Abstract The integration of advanced functions and diverse practical applications calls for multifunctional liquid crystal elastomers (LCEs); however, the structure‐intrinsic luminescence excellent mechanical properties LCEs have not yet been explored. In this study, clusteroluminescence (CL)‐based (CL‐LCEs) are successfully fabricated without depending on large conjugated structures, thereby avoiding redundant organic synthesis aggregation‐caused quenching. experimental theoretical results reveal that secondary amine (–NH–) imine (–C = N–) groups play vital roles in determining presence fluorescence CL‐LCEs. Based above observation, strategy universalization a molecular library constructing CL‐LCEs further demonstrated. Meanwhile, dynamic bond bonds endows CL‐LCE system with rapid self‐healing under mild conditions (70 °C 10 min), stretchability, adaptive programmable characteristics. Furthermore, self‐luminescent performance enables visual detection process. Finally, CL‐based information storage anticounterfeiting realized their fiber actuators fluorescent textiles distinctive chemistry presented work has significant implications elucidating mechanism CL providing new strategies rational design novel LCE materials.

Language: Английский

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