Excited Organic Radicals in Photoredox Catalysis

JACS Au, Journal Year: 2025, Volume and Issue: 5(2), P. 426 - 447

Published: Jan. 29, 2025

Many important synthetic-oriented works have proposed excited organic radicals as photoactive species, yet mechanistic studies raised doubts about whether they can truly function photocatalysts. This skepticism originates from the formation of (photo)redox-active degradation products and picosecond decay electronically radicals, which is considered too short for diffusion-based photoinduced electron transfer reactions. From this perspective, we analyze synthetic transformations where been photocatalysts, comparing their theoretical maximum state potentials with required observed photocatalytic reactivity. We summarize structurally similar photocatalysts indicating different reaction pathways some catalytic systems, addressing cases radical exceed Additionally, perform a kinetic analysis to explain in on subpicosecond time scales. further rationalize potential anti-Kasha reactivity higher states femtosecond lifetimes, highlighting how future photocatalysis advancements could unlock new photochemical pathways.

Language: Английский

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Efficient Energy and Electron Transfer Photocatalysis with a Coulombic Dyad

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25799 - 25812

Published: Sept. 3, 2024

Photocatalysis holds great promise for changing the way value-added molecules are currently prepared. However, many photocatalytic reactions suffer from quantum yields well below 10%, hampering transition lab-scale to large-scale or even industrial applications. Molecular dyads can be designed such that beneficial properties of inorganic and organic chromophores combined, resulting in milder reaction conditions improved reactions. We have developed a novel approach obtaining advantages molecular without time- resource-consuming synthesis these tailored photocatalysts. Simply by mixing cationic ruthenium complex with an anionic pyrene derivative water salt bichromophore is produced owing electrostatic interactions. The long-lived triplet state obtained static quantitative energy transfer preorganized complex. exploited this so-called Coulombic dyad catalysis similar reactivity higher photostability compared reference photosensitizers several photooxygenations. In addition, it was shown system also used maximize yield photoredox This due intrinsically cage escape after photoinduced electron purely compounds heavy atom-containing molecules. combination laboratory-scale as mechanistic irradiation experiments detailed spectroscopic investigations provided deep insights into easy-to-use photocatalyst class.

Language: Английский

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Synergistic performance of porous hierarchical NiO/rGO heterojunction for optimal photocatalytic performance

Chemical Physics Letters, Journal Year: 2025, Volume and Issue: 862, P. 141860 - 141860

Published: Jan. 2, 2025

Language: Английский

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Design and performance investigation of novel efficient photocatalysts PVP-modified PVDF/BiOBr photocatalytic membranes for wastewater treatment

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160781 - 160781

Published: Feb. 1, 2025

Language: Английский

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Intracellular Photocatalytic NADH/NAD(P)H Oxidation for Cancer Drug Development

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 7161 - 7181

Published: Feb. 20, 2025

Photocatalytic cancer therapy (PCT) has emerged as a cutting-edge anticancer mechanism of action, harnessing light energy to mediate the catalytic oxidation intracellular substrates. PCT is significant current importance due its potential address limitations conventional chemotherapy, particularly drug resistance and side effects. This approach offers noninvasive, targeted treatment option by utilizing metal-based photocatalysts induce redox metabolic disorders within cells. The disrupt cell metabolism converting NADH/NAD(P)H NAD+/NAD(P)+ via photoredox processes, altering NAD+/NADH or NAD(P)+/NAD(P)H ratios, which are crucial for cellular metabolism. Ir(III), Ru(II), Re(I), Os(II) demonstrated promising efficacy. Despite these developments, gaps remain in literature translating this new into clinical trials. Perspective critically examines developments research area provides future directions designing efficient PCT.

Language: Английский

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Energy Transfer (EnT)-Mediated Stereoselective Aryl-Heterofunctionalization of Unactivated Alkynes via Radical Rearrangement

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

In this study, we present a novel catalyst-free energy transfer mediated radical rearrangement strategy for the aryl-heterofunctionalization of unactivated alkynes, leading to synthesis polyfunctional olefins with exceptional stereoselectivity. This innovative approach, driven by visible light, exemplifies green chemistry principles eliminating reliance on transition metals, external oxidants, and photocatalysts. The broad applicability our method is demonstrated through successful diverse array compounds, including vinyl sulfones, selenides, sulfides. Preliminary mechanistic insights suggest an mechanism, highlighting efficiency selectivity strategy.

Language: Английский

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Rational design and synthesis of atomically precise nanocluster-based nanocomposites: a step towards environmental catalysis

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Atomically precise metal nanoclusters (NCs) and metal-organic frameworks (MOFs) possess distinct properties that can present challenges in certain applications. However, integrating these materials to create new composite functional has gained significant interest due their unique characteristics through a range of applications, particularly catalysis. Considering MOFs as hosts NCs guests, several synergistic effects have been observed composites, environmental catalytic reactions. the role encapsulated within MOF pore structure is still its infancy. Besides, stabilizing NCs, whether intact ligands or without via host, presents are currently being investigated. This feature article reviews recent advancements synthesis NC@MOF focusing on cutting-edge strategies for selecting roles NC ligands, well characterization

Language: Английский

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Photocatalysis by Mixed Oxides Containing Niobium, Vanadium, Silica, or Tin

Catalysts, Journal Year: 2025, Volume and Issue: 15(2), P. 118 - 118

Published: Jan. 26, 2025

Nb-Sn, V-Sn mixed-metal oxides and Nb-Si, V-Si metal oxide–silicas were successfully synthesized through a “soft” templating method, in which appropriate amounts of salts (either niobium(V) chloride, or vanadium(IV) oxide sulfate hydrate tin(II) chloride dihydrate) tetraethyl orthosilicate (TEOS) mixed with hexadecyltrimethylammonium (HDTA) sodium dodecyl (SDS) solutions to obtain new series mesoporous oxides, followed by calcination at different temperatures. As-obtained samples characterized SEM, TEM, XRD, UV-Vis spectra techniques. The photocatalytic activities the evaluated degradation methyl orange II (MO) under simulated sunlight irradiation. effects species temperature on physicochemical characteristic activity investigated detail. results indicated that, compared pure showed superior performance for MO. A maximum discoloration rate 97.3% (with MO initial concentration 0.6·10−4 mol/dm3) was achieved 300 min NbSiOx material, much higher than that Degussa P25 same conditions. Additionally, tested photochemical oxidation process, i.e., advanced processes (AOPs) treat commercial non-ionic surfactant: propylene ethylene polymer mono(nonylphenyl) ether (N8P7, PCC Rokita). 99.9% 30 material.

Language: Английский

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ESI‐MS‐Visualization of Cyanoarene Photocatalysts by Specific Supramolecular Interaction with Br‐Anion

Chemistry - Methods, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

Abstract Isophthalonitrile derivatives (IPNs) have emerged as promising organic photocatalysts due to their efficiency and accessibility; however, inherent lability under light‐induced conditions poses significant challenges in monitoring transformation pathways. Understanding these pathways is crucial for optimizing photocatalytic processes enhancing reaction efficiency. In this study, we present a novel approach utilizing electrospray ionization mass spectrometry (ESI‐MS) visualize cyanoarene by taking advantage of specific supramolecular interaction with bromide anions. Our findings reveal that ions facilitate the detection IPNs products high sensitivity selectivity, even complex environments. The predominantly occurs gas phase, minimizing interference solution‐based transformations. developed anion‐enhanced (AED‐ESI‐MS) not only provides real‐time insights into photocatalyst behavior but also opens new possibilities detailed mechanistic investigation light‐driven reactions. proposed AED‐ESI‐MS using other anions may offer broad applicability be worth studying further across various systems.

Language: Английский

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Protecting Group-Free Photocatalyzed O-Arylation of Quinic Acid

Tetrahedron Green Chem, Journal Year: 2025, Volume and Issue: unknown, P. 100070 - 100070

Published: Feb. 1, 2025

Language: Английский

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