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

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Title: Photo-release of acetonitrile in ruthenium(II) complexes with various substituted terpyridine ligands.
Authors: Mudrak, Vladyslav1, Lacroix, Pascal G.1 pascal.lacroix@lcc-toulouse.fr, Labra-Vázquez, Pablo1, Tassé, Marine1, Mallet-Ladeira, Sonia1, Malfant, Isabelle1 isabelle.malfant@lcc-toulouse.fr
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. 6/14/2025, Vol. 54 Issue 22, p9021-9031. 11p.
Subjects: Acetonitrile, Ruthenium compounds, Chemical reactions, Electron donor-acceptor complexes, Density functional theory, Crystal structure, Quantum efficiency, Ligands (Chemistry)
Abstract: 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-chargetransfer (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. [ABSTRACT FROM AUTHOR]
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Abstract: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-chargetransfer (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. [ABSTRACT FROM AUTHOR]
ISSN:14779226
DOI:10.1039/d5dt00734h