Counterion Effects in [Ru(bpy)3](X)2-Photocatalyzed Energy Transfer Reactions DOI Creative Commons

Juliette Zanzi,

Zachary Pastorel,

Carine Duhayon

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(8), P. 3049 - 3057

Published: July 24, 2024

Photocatalysis that uses the energy of light to promote chemical transformations by exploiting reactivity excited-state molecules is at heart a virtuous dynamic within community. Visible-light metal-based photosensitizers are most prominent in organic synthesis, thanks their versatile ligand structure tunability allowing adjust photocatalytic properties toward specific applications. Nevertheless, large majority these photocatalysts cationic species whose counterion effects remain underestimated and overlooked. In this report, we show modification X counterions constitutive [Ru(bpy)

Language: Английский

Photocatalytic hydrofluoroalkylation of alkenes with carboxylic acids DOI

Kang‐Jie Bian,

Yen‐Chu Lu, David Nemoto

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(12), P. 1683 - 1692

Published: Nov. 13, 2023

Language: Английский

Citations

75
Photoredox-active Cr(0) luminophores featuring photophysical properties competitive with Ru(II) and Os(II) complexes DOI Creative Commons
Narayan Sinha, Christina Wegeberg, Daniel Häußinger

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(12), P. 1730 - 1736

Published: Aug. 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.

Language: Английский

Citations

55
Recent advances in FeCl3-photocatalyzed organic reactions via hydrogen-atom transfer DOI
Xiaoya Yuan, Congcong Wang, Bing Yu

et al.

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(9), P. 109517 - 109517

Published: Jan. 21, 2024

Language: Английский

Citations

34
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

19
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

18
Iron-Catalyzed Aerobic Carbonylation of Methane via Ligand-to-Metal Charge Transfer Excitation DOI Creative Commons
Hui Pan, Qing An, Binh Khanh

et al.

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

Published: Jan. 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

Language: Английский

Citations

3
Anti-Markovnikov hydro- and deuterochlorination of unsaturated hydrocarbons using iron photocatalysis DOI

Kang‐Jie Bian,

David Nemoto, Ying Chen

et al.

Nature Synthesis, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 2, 2025

Language: Английский

Citations

2
Leveraging Intramolecular π-Stacking to Access an Exceptionally Long-Lived 3MC Excited State in an Fe(II) Carbene Complex DOI
Robert J. Ortiz, Rajarshi Mondal, James K. McCusker

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(2), P. 1694 - 1708

Published: Jan. 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.

Language: Английский

Citations

2
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
Two Birds, One Stone: Microsecond Dark Excited-State Lifetime and Large Cage Escape Yield Afforded by an Iron–Anthracene Molecular Dyad DOI
Felix Glaser,

Simon De Kreijger,

Ludovic Troian‐Gautier

et al.

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

Published: Feb. 28, 2025

Iron photosensitizers represent a holy grail in photochemistry, but their widespread implementation is limited by short excited-state lifetimes and poor cage escape yields. Here, the introduction of an anthracene moiety appended to iron(III) complex allowed solve both limitations generate novel dyad exhibiting extraordinary lifetime 11.5 μs. The key achieving this remarkably long depopulation short-lived iron-centered emissive excited state populate dark triplet located on anthracene-like with spin-forbidden deactivation. Population only occurs ∼10% efficiency acetonitrile still allows expansion scope reactivity accessible iron-based photosensitizers, which now encompasses energy transfer 3O2. In addition, proof-of-principle investigation methyl viologen as electron acceptor, population drastic ten-fold increase yield from 4.5% for unsubstituted 42% molecular dyad. Hence, new provides complementary approach complexes based first-row transition metals alternatives well-established analogues precious metals. We believe that further spectroscopic investigations synthetic modifications acceptor linkage photosensitizer will be use these innovative dyads applications near future.

Language: Английский

Citations

2