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dc.contributor.authorGhosh, Abhik
dc.date.accessioned2021-11-30T12:41:50Z
dc.date.available2021-11-30T12:41:50Z
dc.date.issued2021-08-04
dc.description.abstractOligopyrroles form a versatile class of redox-active ligands and electron reservoirs. Although the stabilization of radicals within oligopyrrolic π systems is more common for macrocyclic ligands, bidentate dipyrrindiones are emerging as compact platforms for one-electron redox chemistry in transition-metal complexes. We report the synthesis of a bis(aqua) palladium(II) dipyrrindione complex and its deprotonation-driven dimerization to form a hydroxo-bridged binuclear complex in the presence of water or triethylamine. Electrochemical, spectroelectrochemical, and computational analyses of the binuclear complex indicate the accessibility of two quasi-reversible ligand-centered reduction processes. The product of a two-electron chemical reduction by cobaltocene was isolated and characterized. In the solid state, this cobaltocenium salt features a folded dianionic complex that maintains the hydroxo bridges between the divalent palladium centers. X-band and Q-band EPR spectroscopic experiments and DFT computational analysis allow assignment of the dianionic species as a diradical with spin density almost entirely located on the two dipyrrindione ligands. As established from the EPR temperature dependence, the associated exchange coupling is weak and antiferromagnetic (J ≈ −2.5 K), which results in a predominantly triplet state at the temperatures at which the measurements have been performed.en_US
dc.identifier.citationGhosh. Ligand-Centered Triplet Diradical Supported by a Binuclear Palladium(II) Dipyrrindione. Inorganic Chemistry. 2021en_US
dc.identifier.cristinIDFRIDAID 1943980
dc.identifier.doi10.1021/acs.inorgchem.1c01691
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/10037/23226
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalInorganic Chemistry
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/NANO2021/262229/Norway/Metallocorroles for photodynamic therapy and bioimaging//en_US
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2021 The Author(s)en_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.titleLigand-Centered Triplet Diradical Supported by a Binuclear Palladium(II) Dipyrrindioneen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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