Decarboxylative Sulfonylation of Carboxylic Acids under Mild Photomediated Iron Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2381 - 2386

Published: March 15, 2024

Organic sulfones are an important class of chemical compounds widely used in many research fields. The direct decarboxylative sulfonylation carboxylic acids is attractive but challenging, particularly when iron as a metal catalyst. Herein, we describe photoinduced iron-catalytic method for the synthesis directly using via radical-based decarboxylation. This protocol mild, highly efficient, and easy-to-operate. A broad scope carbon electrophiles could be well tolerated. mechanism involving iron-catalyzed decarboxylation, radical transfer, single-electron reduction, nucleophilic attack proposed.

Language: Английский

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Iron(III) Carbene Complexes with Tunable Excited State Energies for Photoredox and Upconversion

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: April 10, 2024

Substituting precious elements in luminophores and photocatalysts by abundant first-row transition metals remains a significant challenge, iron continues to be particularly attractive owing its high natural abundance low cost. Most complexes known date face severe limitations due undesirably efficient deactivation of luminescent photoredox-active excited states. Two new iron(III) with structurally simple chelate ligands enable straightforward tuning ground state properties, contrasting recent examples, which chemical modification had minor impact. Crude samples feature two luminescence bands strongly reminiscent complex, this observation was attributed dual luminescence, but our case, there is clear-cut evidence that the higher-energy stems from an impurity only red photoluminescence doublet ligand-to-metal charge transfer (2LMCT) genuine. Photoinduced oxidative reductive electron reactions methyl viologen 10-methylphenothiazine occur nearly diffusion-limited kinetics. Photocatalytic not previously reported for compound class, particular C–H arylation diazonium salts aerobic hydroxylation boronic acids, were achieved low-energy light excitation. Doublet–triplet energy (DTET) 2LMCT anthracene annihilator permits proof principle triplet–triplet annihilation upconversion based on molecular photosensitizer. These findings are relevant development featuring photophysical photochemical properties competitive noble-metal-based compounds.

Language: Английский

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Highly Efficient, Noble-Metal-Free, Fully Aqueous CO₂ Photoreduction Sensitized by a Robust Organic Dye

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 17773 - 17783

Published: June 18, 2024

The development of efficient, selective, and durable CO

Language: Английский

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A comparative study for the efficiency of Pd (II) and Fe (III) complexes as efficient catalysts for synthesis of dihydro‐7H‐5‐thia‐hexaaza‐s‐indacen‐6‐one derivatives supported with DFT approach

Applied Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 38(11)

Published: Aug. 4, 2024

Two novel complexes were synthesized by the reaction of benzothiazol‐pyrimidin‐2‐ylidene ligand (BTP) with Pd (II) and Fe (III) ions. A variety various spectral analytical methods (infrared, 1 H/NMR, 13 C/NMR, electronic spectra, CHN analyses, mass thermogravimetric analysis, magnetic susceptibility) used to characterize investigated BTP its complexes. Correlation experimental results density functional theory calculation proves that geometry BTP‐Fe complex is octahedral, whereas BTP‐Pd square planner. The catalytic effectiveness tested for three‐component condensation process under moderate environmentally friendly conditions. Moreover, effects different Lewis acid, basic, ionic liquid catalysts, as well solvent catalyst dose on investigated. Both catalysts demonstrated strong capability in carefully regulated ideal circumstances. Heterogeneous exhibited superior performance compared homogeneous BTP‐Fe. All products obtained high TOF (turnover frequency) numbers presence these which indicate efficiency synthesis dihydro‐7H‐5‐thia‐hexaaza‐s‐indacen‐6‐one derivatives. two catalysts' recycling reusability reactions also could be reused up seven times efficiency, but (BTP‐Fe) only recycled four times. Furthermore, mechanism was suggested supported DFT calculation. simplicity, safety, stability, use commercially available quick times, excellent yields make it promising future industrial use.

Language: Английский

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Low-energy photoredox catalysis

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 11, 2024

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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Rationalizing Photophysics of Co(III) Complexes with Pendant Pyrene Moieties

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

Published: Jan. 9, 2025

Pendant organic chromophores have been used to improve the photocatalytic performance of many metal-based photosensitizers, particularly in first-row metals, by increasing π conjugation ligands and lowering energy photoactive absorption band. Using a combination spectroscopic studies computational modeling, we rationalize excited state dynamics Co(III) complex containing pendant pyrene moieties, CoL1, where L1 = 1,1′-(4-(pyren-1-yl)pyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium). CoL1 displays higher visible absorptivity, blue luminescence from singlet states compared with CoL0 [L0 1,1′-(pyridine-2,6-diyl)bis(3-methyl-1H-imidazol-3-ium)] which moiety is absent. Emissive properties are highly influenced metal center, reducing fluorescence lifetime 5.9 3.5 ns, shift 43 nm. The lower d orbitals Fe(II) drastically affects character state, resulting mixture intraligand charge-transfer (1ILCT) ligand-to-metal (1LMCT) character. Transient experiments revealed that although dark triplet (3ILPyrene) present, it not efficiently populated possesses short nanosecond-scale lifetime. Instead, metal-centered (3MC) dominate decay path 2.4 ps lifetime, no photoactivity toward oxygen formation or triplet–triplet transfer (TTET). This work shows how various factors can influence excited-state dynamics.

Language: Английский

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Towards a more Sustainable Photocatalysis using Copper and Iron

Current Opinion in Green and Sustainable Chemistry, Journal Year: 2025, Volume and Issue: unknown, P. 100998 - 100998

Published: Jan. 1, 2025

Language: Английский

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Iron(III) Complexes with Luminescence Lifetimes of up to 100 ns to Enhance Upconversion and Photocatalysis

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

Published: Feb. 28, 2025

Iron is the most abundant transition metal element and would be ideal replacement for noble metals in many applications that rely on luminescent long-lived electronically excited states. We show efficient reversible energy transfer between doublet states of iron complexes triplet organic ligands improves storage by up to 350-fold. As a result, luminescence lifetimes 100 ns are achieved, upconversion from red blue light becomes 68 times more yield benchmark photoredox reactions significantly improved. These advances make coordination compounds promising candidates lighting, solar conversion photocatalysis.

Language: Английский

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Investigation of the Excited-State Electron Transfer and Cage Escape Yields Between Halides and a Fe(III) Photosensitizer

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10286 - 10292

Published: April 3, 2024

Excited-state quenching and reduction of [Fe(phtmeimb)2]+, where phtmeimb is phenyl[tris(3-methyl-imidazolin-2-ylidene)]borate, with iodide, bromide, chloride were studied in dichloromethane, acetonitrile, acetonitrile/water 1:1 mixture by means steady-state time-resolved spectroscopic techniques. Quenching rate constants almost diffusion-limited dichloromethane acetonitrile followed the expected periodic trend, i.e., I– > Br– Cl–. Confirmation excited-state reductive electron transfer was only unambiguously obtained when iodide used as a quencher. The cage escape yields, separation geminate radical pair formed upon bimolecular transfer, determined. These yields larger (0.079) than (0.017), no photoproduct could be observed 1:1. This study further emphasizes that solvents low dielectric constant are more suited for productive using Fe(III) photosensitizers 2LMCT excited state.

Language: Английский

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