Ferromagnetically Coupled Chromium(III) Dimer Shows Luminescence and Sensitizes Photon Upconversion DOI Creative Commons
Simon Trippmacher,

Serhiy Demeshko,

Alessandro Prescimone

и другие.

Chemistry - A European Journal, Год журнала: 2024, Номер 30(31)

Опубликована: Март 25, 2024

Abstract There has been much progress on mononuclear chromium(III) complexes featuring luminescence and photoredox activity, but dinuclear have remained underexplored in these contexts until now. We identified a tridentate chelate ligand able to accommodate both meridional facial coordination of chromium(III), either access mono‐ or complex depending reaction conditions. This causes tetragonally distorted primary spheres around complexes, entailing comparatively short excited‐state lifetimes the range 400 800 ns solution at room temperature making photoluminescence essentially oxygen insensitive. The two ions dimer experience ferromagnetic exchange interactions that result high spin ( S =3) ground state with coupling constant +9.3 cm −1 . Photoinduced energy transfer from luminescent ferromagnetically coupled an anthracene derivative results sensitized triplet‐triplet annihilation upconversion. Based proof‐of‐principle studies, seem attractive for development fundamentally new types photophysics photochemistry enabled by magnetic interactions.

Язык: Английский

Host Dependency of Boundary between Strong and Weak Crystal Field Strength of Cr3+ Luminescence DOI
Zhen Song, Peter A. Tanner, Quanlin Liu

и другие.

The Journal of Physical Chemistry Letters, Год журнала: 2024, Номер 15(9), С. 2319 - 2324

Опубликована: Фев. 22, 2024

Cr3+ doped near-infrared phosphors hold significant applications and generate considerable research interest. The critical parameter for assessing the strength of crystal field in Tanabe–Sugano diagram is boundary value Dq/B, representing ratio splitting to Racah B. Nevertheless, there are conflicting values this parameter, as reported various studies, such 2.1, 2.2, 2.3 C/B = 4.5–4.8. Moreover, some with wide-band emissions exhibit a Dq/B that falls within region contradictory strong field. In study, we numerically determine which distinguishes between weak fields. results then demonstrate dependence on host material correlated parameters B C. This work resolves inconsistency emission profile Cr3+, providing researchers more profound comprehension luminescence.

Язык: Английский

Процитировано

33
Reversible Photoinduced Ligand Substitution in a Luminescent Chromium(0) Complex DOI Creative Commons
Narayan Sinha, Joël Wellauer,

Tamar Maisuradze

и другие.

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

Процитировано

10
Iron(III) Carbene Complexes with Tunable Excited State Energies for Photoredox and Upconversion DOI Creative Commons
Joël Wellauer,

Fabienne Ziereisen,

Narayan Sinha

и другие.

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

Процитировано

10
An investigation of the structural-optical properties of Ni2+- bearing borate glass by Li2O addition DOI

Afaf M. Babeer,

Essam A. Elkelany,

Abd El-razek Mahmoud

и другие.

Optical and Quantum Electronics, Год журнала: 2024, Номер 56(4)

Опубликована: Янв. 30, 2024

Язык: Английский

Процитировано

8
Regulation and synthesis of metal–organic frameworks through mixed-ligand strategy: A pathway to enhance adsorption of perfluoroalkyl acids DOI
Yongxing Sun, Kaijun Quan, Jing He

и другие.

Chemical Engineering Journal, Год журнала: 2024, Номер 495, С. 153621 - 153621

Опубликована: Июнь 30, 2024

Язык: Английский

Процитировано

6
The photophysics and applications of molecular rubies DOI
Christoph Förster, Katja Heinze

Advances in inorganic chemistry, Год журнала: 2024, Номер unknown, С. 111 - 159

Опубликована: Янв. 1, 2024

Язык: Английский

Процитировано

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

и другие.

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

Опубликована: Март 23, 2024

We report the electrochemiluminescence (ECL) of a 3d

Язык: Английский

Процитировано

5
Counterion Effects in [Ru(bpy)3](X)2-Photocatalyzed Energy Transfer Reactions DOI Creative Commons

Juliette Zanzi,

Zachary Pastorel,

Carine Duhayon

и другие.

JACS Au, Год журнала: 2024, Номер 4(8), С. 3049 - 3057

Опубликована: Июль 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)

Язык: Английский

Процитировано

5
Additional Insights into the Design of Cr(III) Phosphorescent Emitters Using 6-Membered Chelate Ring Bis(imidazolyl) Didentate Ligands DOI Open Access
Amina Benchohra, Julien Chong, Carlos M. Cruz

и другие.

Inorganic Chemistry, Год журнала: 2024, Номер 63(8), С. 3617 - 3629

Опубликована: Янв. 11, 2024

The interest in Cr(III) complexes has been renewed over the past decades for building practical guidelines design of efficient earth-abundant phosphorescent near-infrared emitters. In that context, we report first family homoleptic tri(didentate) [Cr

Язык: Английский

Процитировано

4
A Near-Infrared Luminescent Cr(III) N-Heterocyclic Carbene Complex DOI Creative Commons
Robert W. Jones, Rory A. Cowin, Iona I. Ivalo

и другие.

Inorganic Chemistry, Год журнала: 2024, Номер 63(19), С. 8526 - 8530

Опубликована: Май 2, 2024

Photoluminescent coordination complexes of Cr(III) are interest as near-infrared spin-flip emitters. Here, we explore the preparation, electrochemistry, and photophysical properties first two examples homoleptic N-heterocyclic carbene Cr(III), featuring 2,6-bis(imidazolyl)pyridine (ImPyIm) 2-imidazolylpyridine (ImPy) ligands. The complex [Cr(ImPy)3]3+ displays luminescence at 803 nm on microsecond time scale (13.7 μs) from a doublet excited state, which transient absorption spectroscopy reveals to be populated within several picoseconds following photoexcitation. Conversely, [Cr(ImPyIm)2]3+ is nonemissive has ca. 500 ps excited-state lifetime.

Язык: Английский

Процитировано

4