Article Dans Une Revue Dalton Transactions Année : 2025

Photo-release of acetonitrile in ruthenium( ii ) complexes with various substituted terpyridine ligands

Résumé

The photo-release of acetonitrile is investigated in a series of ruthenium(II) complexes of the general formula [Ru(R-phtpy)(acac)(MeCN)](PF6) (phtpy stands for 4′-phenyl-2,2′:6′,2′′-terpyridine, and R = Et2N, Me2N, MeO, Me, H, NO2). The experimental quantum yields of photo-release (ϕMeCN = MeCN released/photons absorbed) increases with the donating capability of R, with values ranging from ϕMeCN = 0 (NO2) to ϕMeCN = 0.05 (Et2N). The origin of this effect is investigated computationally using the density functional theory and compared to those reported recently by our group on related [Ru(R-phtpy)(acac)(NO)](PF6) species capable of causing photo-release of NO. In the present case, the capability for MeCN release appears related to the relative energies of the metal-centered (3MC) vs. metal–ligand-charge-transfer (3MLCT) triplet states. The 3MC state, in which the Ru–NC distance is elongated to 4.2 Å, is expected to be responsible for the release. Additionally, four crystal structures are reported for the compounds in which R = Et2N, MeO, H, and NO2.

Fichier principal
Vignette du fichier
Mudrak, Photo-release of acetonitrile in ruthenium(II), 2025.pdf (1.43 Mo) Télécharger le fichier
Origine Publication financée par une institution
Licence

Dates et versions

hal-05093703 , version 1 (02-06-2025)

Licence

Identifiants

Citer

Vladyslav Mudrak, Pascal G Lacroix, Pablo Labra-Vázquez, Marine Tassé, Sonia Mallet-Ladeira, et al.. Photo-release of acetonitrile in ruthenium( ii ) complexes with various substituted terpyridine ligands. Dalton Transactions, 2025, 54 (22), pp.9021-9031. ⟨10.1039/D5DT00734H⟩. ⟨hal-05093703⟩
68 Consultations
98 Téléchargements

Altmetric

Partager

  • More