Construction of Covalent Organic Frameworks via Multicomponent Reactions

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(3), P. 1475 - 1496

Published: Jan. 16, 2023

Multicomponent reactions (MCRs) combine at least three reactants to afford the desired product in a highly atom-economic way and are therefore viewed as efficient one-pot combinatorial synthesis tools allowing one significantly boost molecular complexity diversity. Nowadays, MCRs no longer confined organic have found applications materials chemistry. In particular, can be used prepare covalent frameworks (COFs), which crystalline porous assembled from monomers exhibit broad range of properties applications. This synthetic approach retains advantages small-molecule MCRs, not only strengthening skeletal robustness COFs, but also providing additional driving forces for their crystallization, has been series robust COFs with diverse The present perspective article provides general background discusses types employed COF date, addresses related critical challenges future perspectives inspire MCR-based design new promote further progress this emerging field.

Language: Английский

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Highly Connected Three-Dimensional Covalent Organic Framework with Flu Topology for High-Performance Li-S Batteries

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(14), P. 8141 - 8149

Published: March 29, 2023

Lithium-sulfur batteries (LSBs) have been considered as a promising candidate for next-generation energy storage devices, which however still suffer from the shuttle effect of intermediate lithium polysulfides (LiPSs). Covalent-organic frameworks (COFs) exhibited great potential sulfur hosts LSBs to solve such problem. Herein, pentiptycene-based D2h symmetrical octatopic polyaldehyde, 6,13-dimethoxy-2,3,9,10,18,19,24,25-octa(4'-formylphenyl)pentiptycene (DMOPTP), was prepared and utilized building block toward preparing COFs. Condensation DMOPTP with 4-connected tetrakis(4-aminophenyl)methane affords an expanded [8 + 4] connected network 3D-flu-COF, flu topology. The non-interpenetrated nature topology endows 3D-flu-COF high Brunauer-Emmett-Teller surface area 2860 m2 g-1, large octahedral cavities, cross-linked tunnels in framework, enabling loading capacity (∼70 wt %), strong LiPS adsorption capability, facile ion diffusion. Remarkably, when used host LSBs, delivers 1249 mA h g-1 at 0.2 C (1.0 = 1675 g-1), outstanding rate capability (764 5.0 C), excellent stability, representing one best results among thus far reported COF-based materials being competitive state-of-the-art inorganic materials.

Language: Английский

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Covalent organic frameworks for CO₂ capture: from laboratory curiosity to industry implementation

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(18), P. 6294 - 6329

Published: Jan. 1, 2023

Synergistic developments of covalent organic frameworks and engineering processes can expedite the qualitative leap for net-zero carbon emissions.

Language: Английский

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Postsynthetic Annulation of Three-Dimensional Covalent Organic Frameworks for Boosting CO₂ Photoreduction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15473 - 15481

Published: July 8, 2023

Three-dimensional covalent organic frameworks (3D COFs), with interconnected pores and exposed functional groups, provide new opportunities for the design of advanced materials through postsynthetic modification. Herein, we demonstrate successful annulation 3D COFs to construct efficient CO2 reduction photocatalysts. Two COFs, NJU-318 NJU-319Fe, were initially constructed by connecting hexaphenyl-triphenylene units pyrene- or Fe-porphyrin-based linkers. Subsequently, moieties within postsynthetically transformed into π-conjugated hexabenzo-trinaphthylene (pNJU-318 pNJU-319Fe) enhance visible light absorption photoreduction activity. The optimized photocatalyst, pNJU-319Fe, shows a CO yield 688 μmol g-1, representing 2.5-fold increase compared that unmodified NJU-319Fe. Notably, direct synthesis hexabenzo-trinaphthylene-based COF catalysts was unsuccessful due low solubility conjugated This study not only provides an effective method photocatalysts but also highlights unlimited tunability structural

Language: Английский

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Atomically Dispersed Iron Active Sites on Covalent Organic Frameworks for Artificial Photosynthesis of Hydrogen Peroxide

Advanced Energy Materials, Journal Year: 2024, Volume and Issue: 14(7)

Published: Jan. 11, 2024

Abstract Artificial photosynthesis has been regarded as a promising solution toward solar energy conversion, generating storable and transportable chemical fuels such hydrogen (H 2 ) peroxide O ). However, the design of robust catalytic sites not only affects activity, but also identify atomic‐level correlation between active natural performance. Herein, synthesis method single‐atomic Iron (Fe) anchored on novel covalent organic framework (COF) for production H under visible light irradiation. When benzyl alcohol is most sacrificial agent, state‐of‐the‐art Fe‐based COF exhibits an excellent generation rate 4130 µmol g −1 h , over 5.3 times higher than that pristine COF, achieving apparent quantum yield 6.4% at 420 nm. The enhanced photocatalytic performance ascribed to synergistic effect atomically dispersed Fe hosts, reducing reaction barrier formation * OOH intermediates optimizing adsorption thus promoting two‐electron oxygen reduction (ORR). This work establishes engineering approach build photocatalysts provides in‐depth insight upon ORR mechanism artificial .

Language: Английский

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LaMg6Ga6S16: a chemical stable divalent lanthanide chalcogenide

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

Published: April 5, 2024

Abstract Divalent lanthanide inorganic compounds can exhibit unique electronic configurations and physicochemical properties, yet their synthesis remains a great challenge because of the weak chemical stability. To best our knowledge, although several monoxides epitaxial thin films have been reported, there is no chemically stable crystalline divalent chalcogenide synthesized up to now. Herein, by using octahedra coupling tetrahedra single/double chains construct an octahedral crystal field, we La(II)-chalcogenide, LaMg 6 Ga S 16 . The nature La 2+ cations be identified X-ray photoelectron spectroscopy, absorption near-edge structure electron paramagnetic resonance, while stability confirmed differential thermal scanning, in-situ variable-temperature powder diffraction series solid-state reactions. Owing particular characteristics (5 d 1 ), displays ultrabroad-band green emission at 500 nm, which inaugural instance La(II)-based demonstrating luminescent properties. Furthermore, as crystallizes in non-centrosymmetric space group, P −6, it second-harmonic generation (SHG) active, possessing comparable SHG response with classical AgGaS 2 In consideration its wider band gap ( E g = 3.0 eV) higher laser-induced damage threshold (5×AgGaS also promising nonlinear optical material.

Language: Английский

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The Importance and Discovery of Highly Connected Covalent Organic Framework Net Topologies

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

Published: Jan. 2, 2025

Furthering the field of synthetic organic chemistry from discrete molecules regime to extended structure regime, covalent frameworks (COFs) represent a new genre crystalline porous materials featuring designability with molecular-level precision, well-defined porosity, and exceptional stability imparted by robust linkages reticulating molecules. The topology COFs is principal feature that regulates their functionality usability for emerging technologies. Profound comprehension network topologies maneuvering them toward targeted applications are crucial advancing realm COF research developing novel functional exciting breakthroughs. In this Perspective, we discuss recent pursuits contributing discovery highly connected nets having topologies, assess key challenges achieving such offer insights into current scenario future directions.

Language: Английский

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Synthesis of three-dimensional covalent organic frameworks through a symmetry reduction strategy

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 8, 2025

Language: Английский

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Coordination directed metal covalent organic frameworks

Materials Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 7(15), P. 2995 - 3010

Published: Jan. 1, 2023

The research on coordination directed metal covalent organic frameworks (MCOFs) is systematically reviewed for the continued development of this emerging field.

Language: Английский

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Synthesis of 12-Connected Three-Dimensional Covalent Organic Framework with lnj Topology

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4327 - 4332

Published: Jan. 26, 2024

The structural exploration of three-dimensional covalent organic frameworks (3D COFs) is great significance to the development COF materials. Different from structurally diverse MOFs, which have a variety connectivity (3–24), now valency 3D COFs limited only 4, 6, and 8. Therefore, building blocks with higher necessary path broaden scope structures. Herein, for first time, we designed synthesized 12-connected triptycene-based precursor (triptycene-12-CHO) 12 symmetrical distributions aldehyde groups, also highest reported until now. Based on this unique structure, successfully prepared novel lnj topology (termed 3D-lnj-COF). as-synthesized exhibits honeycomb main pores permanent porosity Brunauer–Emmett–Teller surface area 1159.6 m2 g–1. This work not provides strategy synthesizing precursors high but inspiration enriching COFs.

Language: Английский

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