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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]
Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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DbLabel: Engineering Source
An: 185883934
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  Label: Title
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  Data: Photo-release of acetonitrile in ruthenium(II) complexes with various substituted terpyridine ligands.
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  Data: <searchLink fieldCode="AR" term="%22Mudrak%2C+Vladyslav%22">Mudrak, Vladyslav</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Lacroix%2C+Pascal+G%2E%22">Lacroix, Pascal G.</searchLink><relatesTo>1</relatesTo><i> pascal.lacroix@lcc-toulouse.fr</i><br /><searchLink fieldCode="AR" term="%22Labra-Vázquez%2C+Pablo%22">Labra-Vázquez, Pablo</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Tassé%2C+Marine%22">Tassé, Marine</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Mallet-Ladeira%2C+Sonia%22">Mallet-Ladeira, Sonia</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Malfant%2C+Isabelle%22">Malfant, Isabelle</searchLink><relatesTo>1</relatesTo><i> isabelle.malfant@lcc-toulouse.fr</i>
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  Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. 6/14/2025, Vol. 54 Issue 22, p9021-9031. 11p.
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  Data: <searchLink fieldCode="DE" term="%22Acetonitrile%22">Acetonitrile</searchLink><br /><searchLink fieldCode="DE" term="%22Ruthenium+compounds%22">Ruthenium compounds</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+reactions%22">Chemical reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Electron+donor-acceptor+complexes%22">Electron donor-acceptor complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Crystal+structure%22">Crystal structure</searchLink><br /><searchLink fieldCode="DE" term="%22Quantum+efficiency%22">Quantum efficiency</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: 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]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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RecordInfo BibRecord:
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        Value: 10.1039/d5dt00734h
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      – Code: eng
        Text: English
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        PageCount: 11
        StartPage: 9021
    Subjects:
      – SubjectFull: Acetonitrile
        Type: general
      – SubjectFull: Ruthenium compounds
        Type: general
      – SubjectFull: Chemical reactions
        Type: general
      – SubjectFull: Electron donor-acceptor complexes
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Crystal structure
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      – SubjectFull: Quantum efficiency
        Type: general
      – SubjectFull: Ligands (Chemistry)
        Type: general
    Titles:
      – TitleFull: Photo-release of acetonitrile in ruthenium(II) complexes with various substituted terpyridine ligands.
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            NameFull: Mudrak, Vladyslav
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              M: 06
              Text: 6/14/2025
              Type: published
              Y: 2025
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