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

Title: Photo-release of acetonitrile in ruthenium( ii ) complexes with various substituted terpyridine ligands
Authors: Mudrak, Vladyslav; Lacroix, Pascal, G; Labra-Vázquez, Pablo; Tassé, Marine; Mallet-Ladeira, Sonia; Malfant, Isabelle
Contributors: Laboratoire de chimie de coordination (LCC); Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Université de Toulouse (EPE UT); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Institut de Chimie de Toulouse (ICT); Institut de Recherche pour le Développement (IRD)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP); Communauté d'universités et établissements de Toulouse (Comue de Toulouse)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS); European Project: 101101923,HORIZON-MSCA-2022-Ukraine-ART195-IBA,HORIZON-MSCA-2022-Ukraine-ART195-IBA,MSCA4Ukraine(2022)
Source: ISSN: 1477-9226.
Publisher Information: CCSD; Royal Society of Chemistry
Publication Year: 2025
Collection: Université Toulouse III - Paul Sabatier: HAL-UPS
Subject Terms: [CHIM.COOR]Chemical Sciences/Coordination chemistry; [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry
Description: International audience ; 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.
Document Type: article in journal/newspaper
Language: English
Relation: info:eu-repo/grantAgreement//101101923/EU/MSCA4Ukraine/MSCA4Ukraine
DOI: 10.1039/D5DT00734H
Availability: https://hal.science/hal-05093703; https://hal.science/hal-05093703v1/document; https://hal.science/hal-05093703v1/file/Mudrak,%20Photo-release%20of%20acetonitrile%20in%20ruthenium%28II%29,%202025.pdf; https://doi.org/10.1039/D5DT00734H
Rights: http://creativecommons.org/licenses/by/ ; info:eu-repo/semantics/OpenAccess
Accession Number: edsbas.1BFC5A6E
Database: BASE