Luminescent and Photoredox‐Active Molybdenum(0) Complexes Competitive with Isoelectronic Ruthenium(II) Polypyridines DOI Creative Commons
Tao Jin,

Dorothee Wagner,

Oliver S. Wenger

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(10)

Published: Oct. 27, 2023

Abstract Ruthenium(II) complexes with chelating polypyridine ligands are among the most frequently investigated compounds in photophysics and photochemistry, owing to their favorable luminescence photoredox properties. Equally good photoluminescence performance attractive photocatalytic behavior is now achievable isoelectronic molybdenum(0) complexes. The zero‐valent oxidation state of molybdenum stabilized by carbonyl or isocyanide ligands, metal‐to‐ligand charge transfer (MLCT) excited states analogous those ruthenium(II) can be established. Microsecond MLCT excited‐state lifetimes quantum yields up 0.2 have been achieved solution at room temperature, emission wavelength has become tunable over a large range. stronger photoreductants than polypyridines therefore perform more challenging chemical reductions. triplet nature luminescent allows sensitization photon upconversion via triplet‐triplet annihilation, convert low‐energy input radiation into higher‐energy output fluorescence. This review summarizes current art concerning highlights application potential. Molybdenum roughly 140 times abundant far cheaper ruthenium, hence this research relevant greater context finding sustainable alternatives using precious rare transition metals photochemistry.

Language: Английский

Improved transition metal photosensitizers to drive advances in photocatalysis DOI Creative Commons
Dooyoung Kim, Vinh Q. Dang, Thomas S. Teets

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 15(1), P. 77 - 94

Published: Nov. 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.

Language: Английский

Citations

42
Challenges and Future Perspectives in Photocatalysis: Conclusions from an Interdisciplinary Workshop DOI Creative Commons
Sebastian B. Beil, Sylvestre Bonnet, Carla Casadevall

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(8), P. 2746 - 2766

Published: Aug. 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

Language: Английский

Citations

17
Making Mo(0) a Competitive Alternative to Ir(III) in Phosphors and Photocatalysts DOI Creative Commons
Tao Jin, Narayan Sinha,

Dorothee Wagner

et al.

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

Published: Jan. 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.

Language: Английский

Citations

2
Factors that Impact Photochemical Cage Escape Yields DOI
Matthew Goodwin, John C. Dickenson, Alexia Ripak

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(11), P. 7379 - 7464

Published: May 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.

Language: Английский

Citations

15
Reversible Photoinduced Ligand Substitution in a Luminescent Chromium(0) Complex DOI Creative Commons
Narayan Sinha, Joël Wellauer,

Tamar Maisuradze

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10418 - 10431

Published: April 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.

Language: Английский

Citations

10
Efficient Energy and Electron Transfer Photocatalysis with a Coulombic Dyad DOI
Matthias Schmitz, Maria‐Sophie Bertrams, Arne C. Sell

et al.

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

Citations

9
Low-power, non-coherent light-triggered two-photon absorption via extending the lifetime of the transition state DOI
Le Zeng, Xiangyu Wang, Na Li

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 511, P. 215868 - 215868

Published: April 22, 2024

Language: Английский

Citations

6
Phosphorescent fac-Bis(triarylisocyanide) W(0) and Mo(0) Complexes DOI

Mengwei Yue,

He Jiang, Chao Zou

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(7), P. 3267 - 3282

Published: Feb. 2, 2024

Homoleptic W(0) and Mo(0) complexes containing bis(triarylisocyanide) ligands with bulky substituents were synthesized spectroscopically characterized. Crystallographically determined structures revealed that these are hourglass-like in shape the tridentate adopting a facial coordination mode to metal center. These luminesce fluid solutions solid state. Typically toluene at 298 K, two display emission maximum (lifetime quantum yield) 591 nm (0.83 μs 0.35) 628 (1.04 0.39), similarly, it 575 (0.54 0.15) 617 (0.56 0.23). DFT TDDFT calculations indicated low-energy absorption bands of could be metal-to-ligand charge transfer (MLCT) transitions nature. exhibited reversible M+/0 redox couple −0.70 −0.63 V vs Fc+/0 for −0.86 −0.67 complexes. The excited-state reduction potentials hence estimated −2.91 −2.74 −3.10 −2.81 complexes, indicating they potentially strong photoreductants.

Language: Английский

Citations

5
Electrochemiluminescence of a First‐Row d6 Transition Metal Complex DOI Creative Commons
Egan H. Doeven, Timothy U. Connell, Narayan Sinha

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 23, 2024

We report the electrochemiluminescence (ECL) of a 3d

Language: Английский

Citations

5
Red-Light-Promoted Radical Cascade Reaction to Access Tetralins and Dialins Enabled by Zinc(II)porphyrin, A Light-Flexible Catalyst DOI

Yusuke Okanishi,

Otoki Takemoto,

Sanpou Kawahara

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3929 - 3934

Published: April 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.

Language: Английский

Citations

5