Modulating Linker Conjugation and Flexibility of Aggregation‐Induced Emission Covalent Organic Framework for Enhanced Luminescence DOI Open Access

Haifei Wan,

Xingxiang Wang,

Qinqin Nie

et al.

Advanced Optical Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 6, 2025

Abstract In order to inhibit non‐radiative decay pathways of covalent‐organic frameworks (COFs), a strategy is proposed block intralayer conjugation and interlayer π–π stacking by using flexible aggregation‐induced emission (AIE) building blocks (4′,4′′′,4′′′′′,4′′′′′′′‐(1,2‐ethenediylidene) tetrakis[1,1′‐biphenyl]‐4‐carbaldehyde (TFBE)) connected weakly conjugated linker. By the TFBE as changing flexibility linker, TFBE‐COFs with different luminescence properties are obtained. Experimental theoretical results show that these have high crystallinity large layer spacing, among which photoluminescence quantum yield hydrazone (Hz)‐COF TFBE‐ODH (oxalyl dihydrazide (ODH)) in solid state reaches 26.28%, superior most COFs reported so far. The excellent attributed non‐planar geometry TFBE, inhibits quenching. Moreover, π‐electron delocalization‐induced leaps suppressed further enhances TFBE‐COFs. Hz‐COF exhibits sensing performance for trace tetracycline, detection limit 0.15 µ m . addition, white light‐emitting diodes coated manufactured achieve high‐quality light emission. This study provides new design application high‐emission COFs.

Language: Английский

Covalent Organic Frameworks: Linkage Chemistry and Its Critical Role in The Evolution of π Electronic Structures and Functions DOI
Chunyu He, Shanshan Tao, Ruoyang Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)

Published: March 19, 2024

Covalent organic frameworks (COFs) provide a molecular platform for designing novel class of functional materials with well-defined structures. A crucial structural parameter is the linkage, which dictates how knot and linker units are connected to form two-dimensional polymers layer frameworks, shaping ordered π-array porous architectures. However, roles linkage in development π electronic structures functions remain fundamental yet unresolved issues. Here we report designed synthesis COFs featuring four representative linkages: hydrazone, imine, azine, C=C bonds, elucidate their impacts on evolution functions. Our observations revealed that hydrazone provides non-conjugated connection, while imine azine allow partial conjugation, bond permits full π-conjugation. Importantly, profoundly influences control functions, unraveling its pivotal role determining key properties such as band gap, frontier energy levels, light absorption, luminescence, carrier density mobility, magnetic permeability. These findings highlight significance chemistry offer general transformative guidance framework achieve

Language: Английский

Citations

21
Modified side-chain COFs construct built-in electric fields with low exciton binding energy for photo-reduced uranium DOI
Xin Zhong,

Qian Ling,

Peiling Kuang

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 483, P. 149339 - 149339

Published: Feb. 5, 2024

Language: Английский

Citations

19
Hydrogen Isotope Effect Endows a Breakthrough in Photoluminescent Covalent Organic Frameworks DOI

Mengjia Yuan,

Fuyin Ma,

Lixi Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1250 - 1256

Published: Jan. 8, 2024

Luminescent covalent organic frameworks (LCOFs) have emerged as indispensable candidates in various applications due to their greater tunable emitting properties and structural robustness compared small molecule emitters. An unsolved issue this area is developing highly luminescent LCOFs of which the nonradiative quenching pathways were suppressed much possible. Here, a robust aminal-linked COF (DD-COF) possessing perdeuterated light-emitting monomers was designed synthesized. The solid-state photoluminescence quantum yield DD-COF reaches 81%, significantly outcompeting all state-of-the-art reported so far. exceptional efficiency attributed inhibition different decay, especially from bond vibrations where only substitution by heavier isotope with lower zero-point vibration frequency works. Furthermore, prepared deuterated not boosts higher photostability under UV irradiation but also enables superior fluorescence sensing performance for iodine detection nondeuterated COF.

Language: Английский

Citations

18
Insights into sensing applications of fluorescent covalent organic frameworks DOI

Chengtao Gong,

Chunxing Yan,

Jialiang Liu

et al.

TrAC Trends in Analytical Chemistry, Journal Year: 2024, Volume and Issue: 173, P. 117625 - 117625

Published: Feb. 27, 2024

Language: Английский

Citations

17
Advances in covalent organic frameworks for cancer phototherapy DOI
Nem Singh, Miae Won, Jusung An

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 506, P. 215720 - 215720

Published: Feb. 16, 2024

Language: Английский

Citations

15
Construction of Layer-Blocked Covalent Organic Framework Heterogenous Films via Surface-Initiated Polycondensations with Strongly Enhanced Photocatalytic Properties DOI Creative Commons
Yuxiang Zhao, Shengfei Li, Guangen Fu

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 29, 2024

Imine-linked covalent organic frameworks (COFs) usually show high crystallinity and porosity, while vinyl-linked COFs have excellent semiconducting properties stability. Therefore, achieving the advantages of imine- vinyl-linkages in a single COF material is highly interesting but remains challenging. Herein, we demonstrate fabrication layer-blocked (LB-COF) heterogeneous film that composed through two successive surface-initiated polycondensations. In brief, bottom layer imine-linked was constructed on an amino-functionalized substrate via Schiff-base polycondensation, which unreacted aldehyde edges could be utilized for initiating aldol polycondensation to prepare second film. The resultant LB-COF displays ordering due crystalline templating effect from layer; meanwhile, upper strongly enhance its stability photocatalytic properties. LB also presents superior performance uranium extraction (320 mg g

Language: Английский

Citations

14
Noncovalent Interaction Guided Precise Photoluminescence Regulation of Gold Nanoclusters in Both Isolate Species and Aggregate States DOI

Xiaoxi Luo,

Jie Kong, Hang Xiao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 23, 2024

Designing luminophores bright in both isolate species and aggregate states is of great importance many emerging cutting-edge applications. However, the conventional either emit but quench state or darken species. Here we demonstrate that precise regulation noncovalent interactions can realize states. It firstly discovered intra-cluster interaction enhances emission atomically Au

Language: Английский

Citations

14
One-Dimensional Covalent Organic Framework with Improved Charge Transfer for Enhanced Electrochemiluminescence DOI

Linlin Song,

Wenqiang Gao,

Su Jiang

et al.

Nano Letters, Journal Year: 2024, Volume and Issue: 24(21), P. 6312 - 6319

Published: May 16, 2024

We present a dimensional regulating charge transfer strategy to achieve an enhanced electrochemiluminescence (ECL) by constructing one-dimensional pyrene-based covalent organic framework (1D-COF). The dual-chain-like edge architecture in 1D-COF facilitates the stabilization of aromatic backbones, enhancement electronic conjugations, and decrease energy loss. generates anodic (92.5-fold) cathodic (3.2-fold) signals with tripropylamine (TPrA) K2S2O8 as coreactants, respectively, compared 2D-COF. ECL efficiencies are 2.08- 3.08-fold higher than those 2D-COF, respectively. According density functional theory (DFT), rotational barrier (ΔE) enhances sharply increase dihedral angle, suggesting that restrains intramolecular spin chains, which nonradiative transitions ECL. Furthermore, can be used construct biosensor for sensitive detection dopamine.

Language: Английский

Citations

12
Covalent Organic Framework-Based Photocatalyst for Activation of Peroxymonosulfate: Implications for Degradation of Organic Pollutants DOI
Haocheng Xu, Yang Xu, Yandong Wang

et al.

ACS Applied Nano Materials, Journal Year: 2024, Volume and Issue: 7(3), P. 3071 - 3081

Published: Jan. 30, 2024

Advanced oxidation processes (AOPs), especially high-efficiency activation of peroxymonosulfate (PMS), have aroused great attention based on their excellent performance along with low toxicity in the degradation organic pollutants. Although covalent frameworks (COFs) been explored for PMS-activated AOPs, intrinsic photocatalytic properties are rarely studied this field. Herein, we designed and prepared a fully conjugated carbon framework (TFPT-TCPB COF), which features sp2 C═C linkages, triazine units, nitrile groups, showing potential to PMS as an photocatalyst. Olefin-linked TFPT-TCPB COF showed much higher removal efficiency (k = 0.048 min–1), 3.5 times value rate constant k TFPT-TAPB 0.014 min–1). Meanwhile, photoactive units endowed 2.5 enhancement than TFPB-TCPB embedding only benzene rings 0.013 Furthermore, reaction COF-COOH reached 0.081 min–1, was 69% that 27 g-C3N4, proving positive effects introducing hydrophilic carboxyl groups. Also, high chemical stability, reusability, biotoxicity offered it opportunity marvelous metal-free photocatalyst environment remediation.

Language: Английский

Citations

11
Mesoporous Vinylene‐Linked Covalent Organic Frameworks with Heteroatom‐Tuned Crystallinity and Photocatalytic Behaviors DOI
Mengqi Li,

Xu Chi,

Zixing Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(44)

Published: July 15, 2024

Owing to its prominent π-delocalization and stability, vinylene linkage holds great merits in the construction of covalent organic frameworks (COFs) with promising semiconducting properties. However, carbon-carbon double bond formation reaction always exhibits relatively low reversibility, unfavorable for high crystalline through self-error correction assembling processes. In this work, we report a heteroatom-tuned strategy build up series two-dimensional (2D) vinylene-linked COFs by Knoevenagel condensation an electron-deficient methylthiazolyl-based monomer different triformyl substituted (hetero-)aromatic derivatives. The resulting show high-quality periodic mesoporous structures surface areas. Embedding heteroatoms into backbones enables significantly improving their crystallinity, finely tailoring structures. Upon visible light stimulation, one as-prepared donor-π-acceptor structure could deliver nearly seven-fold increase catalytic activity hydrogen generation as compared other two. Meanwhile, combination crystallinity matched conduction band energy level, such kind can be able selectively generate singlet oxygen superoxide radicals ratio 30 : 1, allowing catalyzing aerobic thioanisole oxidation distinctly tunable activities substituent electronic effect substrates.

Language: Английский

Citations

11