Three-Dimensional Covalent Organic Frameworks with she Topology

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(40), P. 18511 - 18517

Published: Sept. 28, 2022

Reticular chemistry allows the control of crystalline frameworks at atomic precision according to predesigned topological structures. However, only a limited number structures three-dimensional (3D) covalent organic (COFs) have been established. In this work, we developed series 3D COFs with an unprecedented she topology, which were constructed D3d- and D4h-symmetric building blocks. The resulting crystallize in space group Im3̅m, each D3d unit connects six D4h units form noninterpenetrated network uniform pore size 2.0 nm. addition, these exhibited high crystallinity, excellent porosity, good chemical thermal stability. structures, composition, physicochemical properties networks unambiguously characterized. Notably, inbuilt porphyrin render as efficient catalysts for photoredox C-C bond forming photocatalytic carbon dioxide reduction reactions. Thus, work constitutes new approach construction she-net also enhances structural diversity complexity COFs.

Language: Английский

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Porous crystalline materials for memories and neuromorphic computing systems

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(20), P. 7071 - 7136

Published: Jan. 1, 2023

This review highlights the film preparation methods and application advances in memory neuromorphic electronics of porous crystalline materials, involving MOFs, COFs, HOFs, zeolites.

Language: Английский

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Charge and mass transport mechanisms in two-dimensional covalent organic frameworks (2D COFs) for electrochemical energy storage devices

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(3), P. 889 - 951

Published: Jan. 1, 2023

Understanding charge- and mass-transport processes in two-dimensional covalent organic frameworks to design better materials energy storage devices.

Language: Английский

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Nonplanar Rhombus and Kagome 2D Covalent Organic Frameworks from Distorted Aromatics for Electrical Conduction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(11), P. 5042 - 5050

Published: Feb. 21, 2022

Two-dimensional (2D) covalent organic frameworks (COFs) are an emerging class of promising 2D materials with high crystallinity and tunable structures. However, the low electrical conductivity impedes their applications in electronics optoelectronics. Integrating large π-conjugated building blocks into lattices to enhance efficient π-stacking chemical doping is effective way improve COFs. Herein, two nonplanar COFs kagome (DHP-COF) rhombus (c-HBC-COF) have been designed synthesized from distorted aromatics different structures (flexible rigid structure, respectively). DHP-COF shows a highly lattice that hampers stacking, consequently limiting its charge carrier transport properties. Conversely, c-HBC-COF, although concave-convex self-complementary nodes, less does not interfere interlayer π-stacking. Employing time- frequency-resolved terahertz spectroscopy, we unveil charge-carrier mobility up 44 cm2 V-1 s-1, among highest reported for

Language: Английский

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Outstanding Charge Mobility by Band Transport in Two-Dimensional Semiconducting Covalent Organic Frameworks

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7489 - 7496

Published: April 14, 2022

Two-dimensional covalent organic frameworks (2D COFs) represent a family of crystalline porous polymers with long-range order and well-defined open nanochannels that hold great promise for electronics, catalysis, sensing, energy storage. To date, the development highly conductive 2D COFs has remained challenging due to finite π-conjugation along lattice charge localization at grain boundaries. Furthermore, transport mechanism within framework remains elusive. Here, time- frequency-resolved terahertz spectroscopy reveals intrinsically Drude-type band carriers in semiconducting COF thin films condensed by 1,3,5-tris(4-aminophenyl)benzene (TPB) 1,3,5-triformylbenzene (TFB). The TPB-TFB demonstrate high photoconductivity long scattering time exceeding 70 fs room temperature which resembles inorganic materials. This corresponds record carrier mobility 165 ± 10 cm2 V-1 s-1, vastly outperforming state-of-the-art COFs. These results reveal as promising candidates electronics catalysis provide insights into rational design materials efficient transport.

Language: Английский

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Constructing Stable Chromenoquinoline-Based Covalent Organic Frameworks via Intramolecular Povarov Reaction

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(6), P. 2488 - 2494

Published: Feb. 7, 2022

Chemically stable chromenoquinoline (CQ)-based covalent organic frameworks (COFs) were constructed by postsynthetic conversion of imine COFs. The key step an intramolecular Povarov reaction can transform a preintegrated alkyne group to bridge the benzene rings on both sides linkage via chemical bonds, affording ladder-type CQ linkage. This novel approach achieves high cyclization degree 80-90%, which endows CQ-COFs with excellent stability toward strong acid, base, and redox reagents. synthetic be applied various monomers different symmetries functional core moieties. absorption fluorescence intensities are sensitive allows for dual-mode sensing strongly acidic environments.

Language: Английский

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Constructing ambivalent imidazopyridinium-linked covalent organic frameworks

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(5), P. 382 - 392

Published: May 12, 2022

Language: Английский

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Exceptionally high charge mobility in phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type two-dimensional conjugated polymers

Nature Materials, Journal Year: 2023, Volume and Issue: 22(7), P. 880 - 887

Published: June 19, 2023

Abstract Two-dimensional conjugated polymers (2DCPs), composed of multiple strands linear with extended in-plane π-conjugation, are emerging crystalline semiconducting for organic (opto)electronics. They represented by two-dimensional π-conjugated covalent frameworks, which typically suffer from poor π-conjugation and thus low charge carrier mobilities. Here we overcome this limitation demonstrating two phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type 2DCPs (2DCP-MPc, M = Cu or Ni), constructed octaaminophthalocyaninato metal( ii ) naphthalenetetracarboxylic dianhydride polycondensation under solvothermal conditions. The 2DCP-MPcs exhibit optical bandgaps ~1.3 eV highly delocalized π-electrons. Density functional theory calculations unveil strongly dispersive energy bands small electron–hole reduced effective masses ~0.15 m 0 the layer-stacked 2DCP-MPcs. Terahertz spectroscopy reveals band transport Drude-type free carriers in exceptionally high sum mobility electrons holes ~970 cm 2 V −1 s at room temperature, surpassing that reported 2DCPs. This work highlights critical role conjugation enhancing properties great potential high-mobility future

Language: Английский

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Fabrication of an Organic/Inorganic Hybrid TpPa-1-COF/ZnIn₂S₄ S-Scheme Heterojunction for Boosted Photocatalytic Hydrogen Production

ACS Applied Energy Materials, Journal Year: 2023, Volume and Issue: 6(2), P. 1103 - 1115

Published: Jan. 6, 2023

Covalent organic frameworks (COFs) exhibit significant prospects in photocatalytic H2 evolution because of their periodic pore structure, large surface area, and outstanding chemical stability. Nevertheless, a bare COF always suffers from poor photogenerated charge separation efficiency. Hence, it is crucial to design highly effective COF-based heterojunction photocatalysts. In this work, we have successfully prepared an organic/inorganic hybrid TpPa-1-COF/ZnIn2S4 (ZIS) with well-matched S-scheme interfacial charge-transfer channels. The results demonstrate that COF/ZIS-20% has optimal rate, which can reach 853 μmol g–1 h–1 the absence any cocatalyst, 6.2 times TpPa-1-COF when exposed visible light. Moreover, apparent quantum efficiency (AQE) at 420 nm up 2.08%. Density functional theory (DFT) calculations demonstrated presence transfers ZnIn2S4 spontaneously formation electric field area COF/ZIS under ground-state condition. Furthermore, creation tuned built-in drives directional transfer, while electron high reduction, thus synergistically promoting evolution, been by experiments theoretical calculation results. This work provides advanced method for preparation high-efficiency photocatalysts based on matching band structures.

Language: Английский

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Macrocycle‐Based Covalent Organic Frameworks

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(16)

Published: Jan. 6, 2023

Macrocycles with well-defined cavities and the ability to undergo supramolecular interactions are classical materials that have played an essential role in science. However, one of most substantial barriers limiting utilization macrocycles is their aggregation, which blocks active regions. Among many attempted strategies prevent such installing into covalent organic frameworks (COFs), porous stable reticular networks, has emerged as ideal solution. The resulting macrocycle-based COFs (M-COFs) preserve macrocycles' unique activities, enabling applications various fields single-atom catalysis, adsorption/separation, optoelectronics, phototherapy, structural design forming single-layered or mechanically interlocked COFs. properties unmatchable by any combination other substrates, opening a new chapter advanced materials. This review focuses on latest progress concepts, synthesis, properties, M-COFs, presents in-depth outlook challenges opportunities this emerging field.

Language: Английский

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