Spatiotemporal Spectroscopy of Fast Excited-State Diffusion in 2D Covalent Organic Framework Thin Films

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Covalent organic frameworks (COFs), crystalline and porous conjugated structures, are of great interest for sustainable energy applications. Organic building blocks in COFs with suitable electronic properties can feature strong optical absorption, whereas the extended network establish a band structure enabling long-range coherent transport. This peculiar combination both molecular solid-state materials makes an interesting platform to study ultimately utilize photoexcited charge carrier diffusion. Herein, we investigated diffusion two-dimensional COF thin film generated through condensation benzodithiophene-dialdehyde (BDT)

Language: Английский

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Emerging Trends in Conductive Two-Dimensional Covalent Organic Frameworks for Large-Area Electronic Applications

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Two-dimensional covalent organic frameworks (2D COFs) are emerging as promising materials for advanced electronic applications due to their tunable porosity, crystalline order, and π-conjugated structures. These properties enable efficient charge transport bandgap modulation, making 2D COFs strong candidates devices such transistors memristors. However, the practical application of remains limited by challenges in achieving high-quality thin films with large-area uniformity improved crystallinity. This review explores recent advancements fabrication conductive electronics. Various synthesis strategies, including direct growth, vapor-assisted conversion, interfacial methods, discussed context enhancing film quality scalability. The integration into is classified based on operation mechanism─planar vertical field-effect (FETs), electrochemical (ECTs), memristors─to highlight device performance. Looking forward, large-scale production, material compatibility, outlined, alongside potential solutions through innovative techniques collaborative research efforts. By addressing these challenges, poised drive breakthroughs adoption next-generation semiconducting technologies.

Language: Английский

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A Dynamic Covalent Organic Framework with Entangled 2D Layers

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

Dynamic covalent organic frameworks (COFs) represent an emerging class of porous materials with inherent structural flexibility. However, due to the challenges in their synthesis and characterization, research on dynamic COFs remains at early stage requires further exploration. Herein, we report designed a novel COF entangled 2D layers that exhibits interesting behavior response vapor exposure. By employing continuous rotation electron diffraction technique, precisely resolved crystal structures before after adsorption. Structural analysis revealed vapor-induced conformational changes, such as anthracene unit rotation, triggered layer adjustments reduced entanglement angles, leading significant pore structure alterations. This study not only introduces new but also provides foundation for rational design flexibility diverse applications.

Language: Английский

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Regulating the Isomerization Geometry and Energy State of Covalent Organic Frameworks for Enhanced Oxygen Reduction Activity

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

Published: Feb. 19, 2025

Abstract Embedding isomer entities onto crystalline frameworks with precisely defined spatial distributions represents a promising approach to enhancing the efficiency of oxygen reduction reaction (ORR) in fuel cells. However, accurately constructing covalent organic (COFs) regulate energy state effectively remains significant challenge. Herein, an innovative geometric isomerization strategy aimed at minimizing rotational barrier (ΔE), average local ionization (ALIE), and Gibbs free (ΔG) for ORR within COFs is proposed. Based on this strategy, isomeric Py‐COF‐αα 2,2‐substitution, Py‐COF‐ββ 3,3‐substitution, Py‐COF‐αβ 2,3‐substitution mainchain have been obtained. The electronic states intermediate adsorption capabilities are finely tuned through modification, yielding controllable chemical activity. Notably, lower ΔE between thiophenes achieves remarkable performance, evidenced by half‐wave potential 0.77 V vs reversible hydrogen electrode (RHE), surpassing most reported metal‐free electrocatalysts. Combined theoretical prediction situ Raman spectra, it revealed that increased dipole moment non‐uniform charge distribution caused endows pentacyclic‐carbon (thiophene β‐position) far from sulfur atoms efficient catalytic This work has opened up novel paradigm underscores pivotal role regulation facilitating catalysis.

Language: Английский

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Automated Retrosynthesis Planning of Macromolecules Using Large Language Models and Knowledge Graphs

Macromolecular Rapid Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 27, 2025

Abstract Identifying reliable synthesis pathways in materials chemistry is a complex task, particularly polymer science, due to the intricate and often nonunique nomenclature of macromolecules. To address this challenge, an agent system that integrates large language models (LLMs) knowledge graphs proposed. By leveraging LLMs' powerful capabilities for extracting recognizing chemical substance names, storing extracted data structured graph, fully automates retrieval relevant literature, extraction reaction data, database querying, construction retrosynthetic pathway trees, further expansion through additional literature recommendation optimal pathways. considering interdependencies among reactants, novel Multi‐branched Reaction Pathway Search Algorithm (MBRPS) proposed help identify all valid multi‐branched pathways, which arise when single product decomposes into multiple intermediates. In contrast, previous studies are limited cases where at most one intermediate. This work represents first attempt develop automated retrosynthesis planning tailored specially macromolecules powered by LLMs. Applied polyimide synthesis, new approach constructs tree with hundreds recommends optimized routes, including both known

Language: Английский

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Intralayer Anisotropy in Two-Dimensional Conjugated Covalent Organic Frameworks

Research Square (Research Square), Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Two-dimensional (2D) covalent organic frameworks (COFs), as stacked 2D polymers, have emerged promising semiconductors with tunable structures and functionalities, offering significant potential in optoelectronics. Achieving in-plane anisotropy their electronic optical properties is particularly desirable for applications electronics, thermoelectrics, photonics but remains a considerable challenge existing design synthesis approaches. Here, we present novel strategy to introduce intralayer conjugated COFs (2D aniso-c-COFs) using nodes large quadrupole moment imbalances identical linkers. By rationally designing twelve aniso-c-COFs based on benzodithiophene (BDT) nodes, impose highly anisotropic structure that results unprecedented bidirectional charge transport, where electrons holes preferentially migrate along divergent directions. These exhibit remarkable mobilities, reaching up 1200 cm²V^{− 1}s^{− 1} 200 holes, predicted by Boltzmann transport theory. Parallel anisotropy, these materials show pronounced including giant birefringence (|Δn| > 1.0) linear dichroism (|Δk| 1.3), which are COFs, enabling selective polarization control responses. Guided insights, synthesized representative aniso-c-COF, TBDT-P-CN, experimentally demonstrated its high intrinsic mobility. establish unique platform polarization-sensitive optoelectronic applications, paving the way future advancements crystalline materials.

Language: Английский

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Controllable Interfacial Growth of 2D Covalent Organic Framework Films for Organic Electronic Applications

Small Methods, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Abstract Two‐dimensional covalent organic frameworks (2D COFs) are crystalline porous materials with predesignable topologies, periodic structures, and tunable functionalities constructed from molecular building blocks through bonds. Their modular design allows for the integration of various functionalities, making 2D COFs highly suitable optoelectronic applications. COF films have emerged to integrate into devices, avoiding low dispersibility poor processability powder materials. Interfacial polymerization is a blooming method fabricate at liquid‐solid, liquid‐liquid, water‐air, solid‐gas interfaces. Obtaining high‐quality key exploring their performance in electronics. This review first discussed synthetic strategies constructing oriented by interfacial polymerization, including general nucleation‐growth process, field‐induced assembly nucleation‐growth, other methods. The applications electronic devices reviewed, photodetectors, transistors, electrochromic resistive memory, neuromorphic devices. Finally, challenges perspectives synthesizing outlined.

Language: Английский

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Biocomposites of Enzymes and Covalent Organic Frameworks: A Novel Family of Heterogenous Biocatalysis

Chem & Bio Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

Language: Английский

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Semiconducting Polyaromatic Covalent Organic Frameworks Constructed through Self-Aldol Condensation

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 30, 2025

The construction of semiconducting covalent organic frameworks (COFs) via single-component self-polymerization is broad interest in reticular chemistry. Herein, two polyaromatic COFs with all-fused-ring conjugation structures were synthesized through the self-aldol condensation indanone-based building blocks. resulting exhibit n-type properties and exceptional stability under harsh acidic alkaline conditions. electrical conductivity charge carrier mobility reached up to 5.5 × 10-3 S cm-1 0.62 cm2 V-1 s-1, which ranked as highest values among COFs. high crystallinity, intrinsic porosity, excellent conductivity, abundant five-membered rings active sites render these effective metal-free electrocatalysts toward oxygen reduction reaction (ORR). Notably, one shows a half-wave potential 0.77 V conditions, constitutes reported ORR electrocatalysts. In addition, owing strong robustness COFs, they also long-term catalytic durability. This study not only expands diversity but establishes new paradigms for development high-performance process.

Language: Английский

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Cu NPs@covalent organic framework: An efficient photocatalyst for light-assisted selective formylation of phenol derivatives utilizing carbon dioxide

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 582, P. 115154 - 115154

Published: May 2, 2025

Language: Английский

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