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dc.contributor.authorGhosh, Abhik
dc.date.accessioned2021-12-01T13:36:37Z
dc.date.available2021-12-01T13:36:37Z
dc.date.issued2021-09-30
dc.description.abstractA combination of Pt L<sub>3</sub>-edge X-ray absorption spectroscopy (EXAFS and XANES) and DFT (TPSS) calculations have been performed on powder samples of the archetypal platinum porphyrinoid complexes Pt<sup>II</sup>[TpCF<sub>3</sub>PP], Pt<sup>IV</sup>[TpCF<sub>3</sub>PP]Cl<sub>2</sub>, and Pt<sup>IV</sup>[TpCF<sub>3</sub>PC](Ar)(py), where TpCF<sub>3</sub>PP<sup>2-</sup> = meso-tetrakis(p-trifluoromethylphenyl)porphyrinato and TpCF<sub>3</sub>PC<sup>3-</sup> = meso-tris(p-trifluoromethylphenyl)corrolato. The three complexes yielded Pt L<sub>3</sub>-edge energies of 11 566.0 eV, 11 567.2 eV, and 11 567.6 eV, respectively. The 1.2 eV blueshift from the Pt(II) to the Pt(IV) porphyrin derivative is smaller than expected for a formal two-electron oxidation of the metal center. A rationale was provided by DFT-based Hirshfeld which showed that the porphyrin ligand in the Pt(IV) complex is actually substantially oxidized relative to that in the Pt(II) complex. The much smaller blueshift of 0.4 eV, going from Pt<sup>IV</sup>[TpCF<sub>3</sub>PP]Cl<sub>2</sub>, and Pt<sup>IV</sup>[TpCF<sub>3</sub>PC](Ar)(py), is ascribable to the significantly stronger ligand field in the latter compound.en_US
dc.identifier.citationGhosh. X-ray absorption spectroscopy of exemplary platinum porphyrin and corrole derivatives: metal- versus ligand-centered oxidation. RSC Advances. 2021en_US
dc.identifier.cristinIDFRIDAID 1943982
dc.identifier.doi10.1039/D1RA06151H
dc.identifier.issn2046-2069
dc.identifier.urihttps://hdl.handle.net/10037/23240
dc.language.isoengen_US
dc.publisherRoyal Society of Chemistryen_US
dc.relation.journalRSC Advances
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/NANO2021/262229/Norway/Metallocorroles for photodynamic therapy and bioimaging//en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/?/324139/Norway/?/?/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.titleX-ray absorption spectroscopy of exemplary platinum porphyrin and corrole derivatives: metal- versus ligand-centered oxidationen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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