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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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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Improved transition metal photosensitizers to drive advances in photocatalysis

Chemical Science, Год журнала: 2023, Номер 15(1), С. 77 - 94

Опубликована: Ноя. 24, 2023

To function effectively in a photocatalytic application, photosensitizer's light absorption, excited-state lifetime, and redox potentials, both the ground state excited state, are critically important. The absorption profile is particularly relevant to applications involving solar harvesting, whereas potentials lifetimes determine thermodynamics, kinetics, quantum yields of photoinduced processes. This perspective article focuses on synthetic inorganic organometallic approaches optimize these three characteristics transition-metal based photosensitizers. We include our own work areas, which has focused extensively exceptionally strong cyclometalated iridium photoreductants that enable challenging reductive photoredox transformations organic substrates, more recent led improved harvesting charge-transfer copper(i) chromophores, an emerging class earth-abundant compounds solar-energy applications. also highlight many other complementary strategies for optimizing parameters representative examples from literature. It remains significant challenge simultaneously all at once, since improvements one often come detriment others. These inherent trade-offs obviate or circumvent them discussed throughout.

Язык: Английский

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Reversible Photoinduced Ligand Substitution in a Luminescent Chromium(0) Complex

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10418 - 10431

Опубликована: Апрель 8, 2024

Light-triggered dissociation of ligands forms the basis for many compounds interest photoactivated chemotherapy (PACT), in which medicinally active substances are released or "uncaged" from metal complexes upon illumination. Photoinduced ligand is usually irreversible, and recent studies performed context PACT focused on ruthenium(II) polypyridines related heavy complexes. Herein, we report a first-row transition complex, photoinduced spontaneous recoordination unit occurs. Two scorpionate-type tridentate chelates provide an overall six-coordinate arylisocyanide environment chromium(0). Photoexcitation causes decoordination one these six ligating units coordination solvent molecule, at least tetrahydrofuran 1,4-dioxane solvents, but far less toluene, below detection limit cyclohexane. Transient UV-vis absorption spectroscopy quantum chemical simulations point to directly excited metal-to-ligand charge-transfer state. Owing chelate design substitution lability metal, photodissociated can occur spontaneously millisecond time scale. This work provides insight into possible self-healing mechanisms counteracting unwanted photodegradation processes seems furthermore relevant contexts photoswitching (photo)chemical information storage.

Язык: Английский

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Efficient Energy and Electron Transfer Photocatalysis with a Coulombic Dyad

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(37), С. 25799 - 25812

Опубликована: Сен. 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.

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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Low-power, non-coherent light-triggered two-photon absorption via extending the lifetime of the transition state

Coordination Chemistry Reviews, Год журнала: 2024, Номер 511, С. 215868 - 215868

Опубликована: Апрель 22, 2024

Язык: Английский

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Red-Light-Promoted Radical Cascade Reaction to Access Tetralins and Dialins Enabled by Zinc(II)porphyrin, A Light-Flexible Catalyst

Organic Letters, Год журнала: 2024, Номер 26(18), С. 3929 - 3934

Опубликована: Апрель 26, 2024

[5,15-Bis(pentafluorophenyl)-10,20-diphenylporphinato]zinc(II) (1), a metalloporphyrin derivative that was recently reported as an efficient photocatalyst driven by blue LEDs our group, found to catalyze red-light-promoted (630 nm LEDs) radical cascade reaction of N-3-arylpropionyloxyphthalimides with radicophiles including electron-deficient alkenes and alkynes, providing access range functionalized tetralin dialin derivatives. The catalyzed 1 took place via oxidative quenching cycle in DMSO, where no sacrificial electron donor required, uncovering unique solvent effect capable promoting the porphyrin catalysis.

Язык: Английский

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Electrochemiluminescence of a First‐Row d⁶ Transition Metal Complex

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 23, 2024

We report the electrochemiluminescence (ECL) of a 3d

Язык: Английский

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Coulomb interactions for mediator-enhanced sensitized triplet–triplet annihilation upconversion in solution

Nanoscale, Год журнала: 2023, Номер 16(1), С. 123 - 137

Опубликована: Ноя. 29, 2023

An energy transfer cascade in a three-component upconversion system improves the emission quantum yield and reduces intrinsic filter effects. Investigations of molecular interactions are combined with lab-scale applications photocatalysis.

Язык: Английский

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