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

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

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