Photocatalytic hydrofluoroalkylation of alkenes with carboxylic acids

Nature Chemistry, Год журнала: 2023, Номер 15(12), С. 1683 - 1692

Опубликована: Ноя. 13, 2023

Язык: Английский

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Photoredox-active Cr(0) luminophores featuring photophysical properties competitive with Ru(II) and Os(II) complexes

Nature Chemistry, Год журнала: 2023, Номер 15(12), С. 1730 - 1736

Опубликована: Авг. 14, 2023

Coordination complexes of precious metals with the d6 valence electron configuration such as Ru(II), Os(II) and Ir(III) are used for lighting applications, solar energy conversion photocatalysis. Until now, made from abundant first-row transition competitive photophysical photochemical properties have been elusive. While previous research efforts focused mostly on Fe(II), we disclose that isoelectronic Cr(0) gives access to higher photoluminescence quantum yields excited-state lifetimes when compared any other metal complex reported so far. The luminescence behaviour metal-to-ligand charge transfer excited states these is polypyridines. With complexes, become exploitable in photoredox catalysis, benchmark chemical reductions proceed efficiently under low-energy red illumination. Here demonstrate appropriate molecular design strategies open up new perspectives photophysics photochemistry metals.

Язык: Английский

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Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer

Chinese Chemical Letters, Год журнала: 2024, Номер 35(9), С. 109517 - 109517

Опубликована: Янв. 21, 2024

Язык: Английский

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Challenges and Future Perspectives in Photocatalysis: Conclusions from an Interdisciplinary Workshop

JACS Au, Год журнала: 2024, Номер 4(8), С. 2746 - 2766

Опубликована: Авг. 8, 2024

Photocatalysis is a versatile and rapidly developing field with applications spanning artificial photosynthesis, photo-biocatalysis, photoredox catalysis in solution or supramolecular structures, utilization of abundant metals organocatalysts, sustainable synthesis, plastic degradation. In this Perspective, we summarize conclusions from an interdisciplinary workshop young principal investigators held at the Lorentz Center Leiden March 2023. We explore how diverse fields within photocatalysis can benefit one another. delve into intricate interplay between these subdisciplines, by highlighting unique challenges opportunities presented each multidisciplinary approach drive innovation lead to solutions for future. Advanced collaboration knowledge exchange across domains further enhance potential photocatalysis. Artificial photosynthesis has become promising technology solar fuel generation, instance, via water splitting CO

Язык: Английский

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Anti-Markovnikov hydro- and deuterochlorination of unsaturated hydrocarbons using iron photocatalysis

Nature Synthesis, Год журнала: 2025, Номер unknown

Опубликована: Янв. 2, 2025

Язык: Английский

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Iron-Catalyzed Aerobic Carbonylation of Methane via Ligand-to-Metal Charge Transfer Excitation

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 6, 2025

The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization inert C-H bonds, facilitating use nonprecious metal catalysts in demanding transformations. Notably, aerobic carbonylation methane to acetic acid remains formidable due rapid oxidation methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT achieve exceptional C2/C1 selectivity through synergistic photoexcitation, generation, and carbonylation. Mechanistic studies highlight critical roles Fe(II) Fe-carbonyl complexes bypassing via a rebound-like pathway, unlocking unprecedented efficiency

Язык: Английский

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Leveraging Intramolecular π-Stacking to Access an Exceptionally Long-Lived ³MC Excited State in an Fe(II) Carbene Complex

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(2), С. 1694 - 1708

Опубликована: Янв. 6, 2025

The ability to manipulate excited-state decay cascades using molecular structure is essential the application of abundant-metal photosensitizers and chromophores. Ligand design has yielded some spectacular results elongating charge-transfer excited state lifetimes Fe(II) coordination complexes, but triplet metal-centered (3MC) states─recently demonstrated be critical photoactivity isoelectronic Co(III) polypyridyls─have date remained elusive, with temporally isolable examples limited picosecond regime. With this report, we show how strong-field donors intramolecular π-stacking can conspire stabilize a long-lived 3MC for remarkable 4.1 ± 0.3 ns in fluid solution at ambient temperature. Analysis variable-temperature time-resolved absorption data theoretical models ranging from Arrhenius semiclassical Marcus theory, combined computational modeling X-ray crystallography, reveal Jahn-Teller stabilized high activation barrier ground-state recovery. net result chromophore lifetime that orders magnitude longer than anything yet observed an complex.

Язык: Английский

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Making Mo(0) a Competitive Alternative to Ir(III) in Phosphors and Photocatalysts

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Iridium is used in commercial light-emitting devices and photocatalysis but among the rarest stable chemical elements. Therefore, replacing iridium(III) photoactive molecular complexes with abundant metals of great interest. First-row transition generally tend to yield poorer luminescence behavior, it remains difficult obtain excited states redox properties that exceed those noble-metal-based photocatalysts. Here, we overcome these challenges a nonprecious second-row metal. Tailored coordination spheres for molybdenum(0) lead photoluminescence quantum yields rival photochemical reduction reactions not normally achievable become possible. These developments open new perspectives noble lighting applications Earth-abundant advancing metal-based beyond current limits.

Язык: Английский

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The great strides of iron photosensitizers for contemporary organic photoredox catalysis: On our way to the holy grail?

Coordination Chemistry Reviews, Год журнала: 2023, Номер 500, С. 215522 - 215522

Опубликована: Ноя. 9, 2023

Язык: Английский

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Factors that Impact Photochemical Cage Escape Yields

Chemical Reviews, Год журнала: 2024, Номер 124(11), С. 7379 - 7464

Опубликована: Май 14, 2024

The utilization of visible light to mediate chemical reactions in fluid solutions has applications that range from solar fuel production medicine and organic synthesis. These are typically initiated by electron transfer between a photoexcited dye molecule (a photosensitizer) redox-active quencher yield radical pairs intimately associated within solvent cage. Many these radicals undergo rapid thermodynamically favored "geminate" recombination do not diffuse out the cage surrounds them. Those escape useful reagents may subsequent important above-mentioned applications. process factors determine yields remain poorly understood despite decades research motivated their practical fundamental importance. Herein, state-of-the-art on light-induced appeared since seminal 1972 review J. P. Lorand entitled "The Cage Effect" is reviewed. This also provides some background for those new field discusses both homolytic bond photodissociation bimolecular induced reactions. concludes with key goals directions future promise elevate this very vibrant even greater heights.

Язык: Английский

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