Carbon Quantum Dots: Synthesis, Structure, Properties, and Catalytic Applications for Organic Synthesis

Catalysts, Journal Year: 2023, Volume and Issue: 13(2), P. 422 - 422

Published: Feb. 16, 2023

Carbon quantum dots (CQDs), also known as carbon (CDs), are novel zero-dimensional fluorescent carbon-based nanomaterials. CQDs have attracted enormous attention around the world because of their excellent optical properties well water solubility, biocompatibility, low toxicity, eco-friendliness, and simple synthesis routes. numerous applications in bioimaging, biosensing, chemical sensing, nanomedicine, solar cells, drug delivery, light-emitting diodes. In this review paper, structure CQDs, physical properties, approach, application a catalyst multisubstituted 4H pyran, azide-alkyne cycloadditions, degradation levofloxacin, selective oxidation alcohols to aldehydes, removal Rhodamine B, H-bond catalysis Aldol condensations, cyclohexane oxidation, intrinsic peroxidase-mimetic enzyme activity, amines alcohols, ring opening epoxides discussed. Finally, we discuss future challenges research field. We hope paper will open new channel for organic synthesis.

Language: Английский

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Donor–Acceptor Mixed-Naphthalene Diimide-Porphyrin MOF for Boosting Photocatalytic Oxidative Coupling of Amines

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(8), P. 5723 - 5732

Published: April 12, 2023

Integrating electron donor and acceptor chromophores as ligands within one MOF for light harvesting photocatalysis appears to be a major synthesis challenge. Meanwhile, high-efficiency selective aerobic oxidative coupling of amines imines under mild conditions is highly desirable scientific industrial fields. Herein, via facile one-pot synthetic strategy, an porphyrin ligand 5,15-di(p-benzoato)porphyrin (H2DPBP) was successfully integrated into naphthalene diimide (electron acceptor)-based Zr-MOF (Zr-NDI) construct mixed-ligand (Zr-NDI-H2DPBP) benefiting from the two with similar geometry connectivity. When utilized heterogeneous photocatalyst benzylamine at room temperature, prepared Zr-NDI-H2DPBP exhibited boosted imine generation rate (136 mmol g–1 h–1) far exceeding those other noble-metal-free photocatalysts can applied various derivatives. Furthermore, results experiments density functional theory calculations, photocatalytic performance attributed photoinduced transfer H2DPBP NDI energy facilitated by photosensitized irradiation, which effectively improve electron–hole separation efficiency generate abundant reactive active species superoxide radical (O2•–) singlet oxygen (1O2), respectively. This work provides avenue chromophore-based light-harvesting systems utilizing MOFs platforms boost solar-energy conversion.

Language: Английский

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Enhanced Photoinduced Baeyer–Villiger Oxidation of Ketones by Introducing Trinuclear Ruthenium Clusters into Polyoxometalate-Based Metal–Organic Frameworks

Chemistry of Materials, Journal Year: 2023, Volume and Issue: 35(10), P. 3941 - 3950

Published: May 12, 2023

The development of solar-driven organic synthesis processes as an alternative to conventional thermo-catalytic technologies is great research significance in academia and industry. Herein, we looked into the photoinduced Baeyer–Villiger oxidation cyclohexanone based on Mukaiyama method for first time. We fabricated a crystalline polyoxometalate-based metal–organic framework photocatalyst, CR-SiW12, which represents example trinuclear ruthenium clusters involved construction frameworks. was efficiently converted ε-caprolactone under visible light (>400 nm) irradiation with CR-SiW12 catalyst, reaction turnover number frequency recorded 941 274.5 h–1, respectively, apparent quantum yield at 465 nm measured be 8.4%. Moreover, exhibited high structural stability reusability where remained 91.3% after five consecutive cycles. This work offers promising strategy accomplishing reactions green conditions.

Language: Английский

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Mesoporous Mixed-Metal–Organic Framework Incorporating a [Ru(Phen)₃]²⁺ Photosensitizer for Highly Efficient Aerobic Photocatalytic Oxidative Coupling of Amines

ACS Applied Materials & Interfaces, Journal Year: 2023, Volume and Issue: 15(25), P. 30320 - 30331

Published: June 13, 2023

[Ru(Phen)3]2+ (phen = phenanthroline) as a very classical photosensitizer possesses strong absorption in the visible range and facilitates photoinduced electron transfer, which plays vital role regulating photochemical reactions. However, it remains significant challenge to utilize more adequately exploit efficiently ruthenium-based materials due uniqueness, scarcity, nonrenewal of noble metal. Here, we integrate intrinsic advantages mesoporous metal-organic frameworks (meso-MOFs) into photosensitizer-embedded heterometallic Ni(II)/Ru(II) meso-MOF (LTG-NiRu) via metalloligand approach. LTG-NiRu, with an extremely robust framework large one-dimensional (1D) channel, not only makes ruthenium units anchored inner wall tubes circumvent problem product/catalyst separation recycling catalysts heterogeneous systems but also exhibits exceptional activities for aerobic photocatalytic oxidative coupling amine derivatives general photocatalyst. The conversion light-induced reaction various benzylamines is ∼100% 1 h, than 20 chemical products generated by cycloaddition N-substituted maleimides N,N-dimethylaniline can be synthesized easily presence LTG-NiRu upon light irradiation. Moreover, experiments demonstrate that excellent photocatalyst high stability reusability. represents great potential photosensitizer-based platform efficient oxidation function convenient gram-scale synthesis.

Language: Английский

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PW12-M@COFs as efficient photocatalysts for visible-light-driven oxidation of various sulfides and degradation of chemical warfare agent simulant

Applied Catalysis A General, Journal Year: 2023, Volume and Issue: 662, P. 119283 - 119283

Published: May 27, 2023

Language: Английский

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[Ru(bpy)₃]²⁺ Derivatives-Incorporated POM@MOFs with Good Photocatalytic Activity for Visible-Light-Driven Oxidative Coupling of Amines to Imines

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

Published: April 8, 2025

Two novel POM@MOFs, {H3Zn2.5(H2O)10[Ru(dcbpy)3][PMo11VIMoVO40]}·2H2O (RuZn-PMo) and {H3Ni2.5(H2O)12[Ru(dcbpy)3][PMo11VIMoVO40]}·5H2O (RuNi-PMo), have been synthesized through a traditional hydrothermal method. They are composed of [Ru(bpy)3]2+-derived hexa-carboxylate Keggin-type anion [PMo11VIMoVO40]4-. In addition, their structures were well characterized by various spectroscopic methods. Under the irradiation visible light (λ > 400 nm), RuZn-PMo RuNi-PMo as heterogeneous photocatalysts showed efficient photocatalytic performance in coupling reaction amines, with TONs 451 454, respectively. Moreover, exhibited excellent reusability stability after three continuous cycles. Besides, EPR measurements performed to elucidate mechanism.

Language: Английский

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Difunctional POM-based artificial leaf with directed charge transfer to promote photosynthetic overall reaction

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 496, P. 153637 - 153637

Published: July 14, 2024

Language: Английский

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Visible-Light-Responsive 2D Photocatalysts Assembled by Evans–Showell-Type POMs and Metalloviologen Frameworks for Sulfide–Sulfoxide Transformation

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(26), P. 10120 - 10130

Published: June 22, 2023

Sulfide-sulfoxide aerobic photo-oxidation is of great interest in organic and medicinal chemistry; however, developing efficient facile heterogeneous photocatalytic systems without additional additives remains challenging. Herein, we intentionally designed synthesized two polyoxometalate (POM)-based metalloviologen frameworks, formulated as [MII(4-PBPY)2(H2O)][MII(H2O)4][CoIII2MoVI10H4O38]·nH2O (M = Cu, n 10 for 1; M Co, 11 2), prepared by the mild one-step synthesis strategy characterized detail. X-ray single-crystal diffraction analysis shows that they present a two-dimensional layered structure formed parallel layers pillared dimeric Evans-Showell-type POMs. The connection POM to framework enables easier flow electrons port, which can theoretically further induce O2 generate reactive oxygen species (O2•-) oxidize substrates form target products. As expected, both 1 2 exhibit outstanding activity oxidation sulfides. Within 6 h, methyl phenyl sulfide be quantitatively converted into sulfoxide. in-depth mechanism reveals there also synergistic energy-transfer pathway catalytic system addition electron-transfer pathway. In addition, corresponding well maintained after at least cycle experiments.

Language: Английский

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Synthesis and Theoretical and Photophysical Study on a Series of Neutral Ruthenium(II) Complexes with Donor–Metal–Accepter Configuration

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(4), P. 1476 - 1487

Published: Jan. 19, 2023

In order to construct a new type of ruthenium(II) terpyridine complexes with activated triplet metal-centered (3MC) states, as well stabilized metal-to-ligand charge transfer (3MLCT) conducive fine emissive performances, Ru-1, Ru-2, Ru-3, and Ru-4 were synthesized. Compared the [Ru(terpyridine)2]2+ prototype (0.25 ns), this series exhibit lengthened excited state lifetime (43.3 ns for 52.7 43.6 53.4 Ru-4). Interfragment analysis illustrates electron direction four complexes, manifesting their intramolecular characteristic. When excited, lowest-lying states are assigned 3MLCT based on spin-density surface distribution. The singlet thoroughly studied by UV-visual absorption nanosecond time-resolved transient spectra, respectively. Photoluminescence spectra revealed weak broadband near-infrared emission at room temperature red phosphorescence 77 K. low molecular weight good thermal stability make Ru-1 Ru-2 suitable vaporization coating, while solubility in common organic solvents makes Ru-3 solution processing. Furthermore, intrinsic electroneutrality favorable energy levels endow them potential be applied optoelectronic field.

Language: Английский

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Cationic Ruthenium for C-H Activation Reactions

Current Organic Chemistry, Journal Year: 2023, Volume and Issue: 27(1), P. 55 - 61

Published: Jan. 1, 2023

Abstract: C-C bond formation in a regiospecific and atom economic manner has been challenge, which was tried to be resolved through directing group organometals-based C-H activation strategy. The its advantages are well explored the field of organic chemistry, with relevant mechanistic approach regioselective aryl group. Organometals like Ru, Pd, Pt, Ni, etc. have best discovered for innate where pre-activation inert not found necessary. In progress these reactions organometals, various forms ruthenium different groups as substrate. Here we focusing mainly on cationic ruthenium, use activation. shows unique characteristics reactivity an substrate, is highlighted here examples. its, role also exemplified diagrammed representation catalytic cycle. application will give complete knowledge about

Language: Английский

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