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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Unleashing the potentiality of metals: synergistic catalysis with light and electricity

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(14), С. 4024 - 4040

Опубликована: Янв. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Апрель 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.

Язык: 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, Год журнала: 2025, Номер unknown

Опубликована: Фев. 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.

Язык: 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, Год журнала: 2024, Номер 146(15), С. 10286 - 10292

Опубликована: Апрель 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.

Язык: Английский

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Aminomethylations of electron-deficient compounds—bringing iron photoredox catalysis into play

Chemical Science, Год журнала: 2024, Номер 15(30), С. 12077 - 12085

Опубликована: Янв. 1, 2024

Electron transfer to the 2 LMCT state of a photoactive complex based on Earth-abundant iron has been used drive photocatalytic aminomethylation reactions by generation α-aminoalkyl radicals and underlying mechanism investigated.

Язык: Английский

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Factors Controlling Cage Escape Yields of Closed- and Open-Shell Metal Complexes in Bimolecular Photoinduced Electron Transfer

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22818 - 22828

Опубликована: Июль 30, 2024

The cage escape yield, i.e., the separation of geminate radical pair formed immediately after bimolecular excited-state electron transfer, was studied in 11 solvents using six Fe(III), Ru(II), and Ir(III) photosensitizers tri-p-tolylamine as donor. Among all complexes, largest yields (0.67–1) were recorded for photosensitizer, showing highest potential a photocatalyst photoredox catalysis. These dropped to values around 0.65 both Ru(II) 0.38 Os(II) photosensitizer. Interestingly, open-shell Fe(III) small (<0.1) with dielectric constant greater than 20 but shown reach up 0.58 low constants. results presented herein on closed-shell suggest that rate triplet–singlet intersystem crossing within manifold states implies charge recombination toward ground state is spin-forbidden process, favoring large are not influenced by effects. Geminate metal such two herein, no longer process becomes highly sensitive solvent Altogether, this study provides general guidelines factors influencing reactivity prototypical also allows one foresee great development 2LMCT excited catalysis, providing constants used.

Язык: Английский

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From photons to reactions: key concepts in photoredox catalysis

Chem Catalysis, Год журнала: 2024, Номер unknown, С. 101110 - 101110

Опубликована: Сен. 1, 2024

Язык: Английский

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Simulation of Ultrafast Excited-State Dynamics in Fe(II) Complexes: Assessment of Electronic Structure Descriptions

Journal of Chemical Theory and Computation, Год журнала: 2025, Номер unknown

Опубликована: Янв. 3, 2025

The assessment of electronic structure descriptions utilized in the simulation ultrafast excited-state dynamics Fe(II) complexes is presented. Herein, we evaluate performance RPBE, OPBE, BLYP, B3LYP, B3LYP*, PBE0, TPSSh, CAM-B3LYP, and LC-BLYP (time-dependent) density functional theory (DFT/TD-DFT) methods full-dimensional trajectory surface hopping (TSH) simulations carried out on linear vibronic coupling (LVC) potentials. We exploit existence time-resolved X-ray emission spectroscopy (XES) data for [Fe(bmip)2]2+ [Fe(terpy)2]2+ prototypes between metal-to-ligand charge-transfer (MLCT) metal-centered (MC) states, which serve as a reference to benchmark calculations (bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, terpy 2,2′:6′,2″-terpyridine). results show that simulated population MLCT MC states with various spin multiplicities (singlet, triplet, quintet) highly depend DFT/TD-DFT method, percentage exact (Hartree–Fock) exchange being governing factor. Importantly, B3LYP* TPSSh are only satisfactory performance, best reproducing experimentally resolved both complexes, signaling an optimal balance description MLCT–MC energetics. This work demonstrates power combining TSH/LVC experimental potential energy surfaces.

Язык: Английский

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