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dc.contributor.authorCao, Rui
dc.contributor.authorThomas, Kolle E.
dc.contributor.authorGhosh, Abhik
dc.contributor.authorSarangi, Ritimukta
dc.date.accessioned2021-02-05T13:21:24Z
dc.date.available2021-02-05T13:21:24Z
dc.date.issued2020-05-29
dc.description.abstractA combination of Cr K-edge XAS and DFT calculations have been performed on archetypal chromium porphyrinoid complexes Cr<sup>IV</sup>[TMP]O (<b>2</b>) and Cr<sup>V</sup>[TPC]O (<b>3</b>), and the results have been compared to the reference compound Cr<sup>III</sup>[TPP]Cl (<b>1</b>), where TPP<sup>2−</sup>, TMP<sup>2−</sup>, and TPC<sup>3−</sup> are the anions of <i>meso</i>-tetraphenylporphyrin, <i>meso</i>-tetramesitylporphyrin, and <i>meso</i>-triphenylcorrole, respectively. The intensity-weighted average energy position in <b>1</b> (5990.9 eV), <b>2</b> (5992.0 eV) and <b>3</b> (5992.6 eV) are consistent with increasing the metal oxidation state along the series. EXAFS and theoretical analysis of <b>2</b> and <b>3</b> reveal that the Cr–O bond is longer and weaker in <b>3</b> relative to <b>2</b>, despite the structural similarity and increase in oxidation state in <b>3</b>. This is also reflected in a comparison of the Cr K-pre-edge transitions. The roughly twenty-fold increase in intensity in the two oxo complexes is unsurprising and well-precedented for other first-row transition metals. However, although <b>3</b> had greater overall intensity, the intensity of transitions along the Cr–O bond is greater. EXAFS, DFT and TDDFT analyses show that the more contracted N<sub>4</sub> core of the corrole results in a greater out-of-plane displacement of the Cr in <b>3</b> relative to <b>2</b>, which in turn accentuates the lower local symmetry of the Cr in <b>3</b> relative to <b>2</b>. This difference helps us to appreciate the TDDFT result that whereas two 1s→ 3d<sub>z2</sub> transitions make up the majority of the intensity in the pre-edge of <b>2</b>, the pre-edge of <b>3</b> also includes fairly intense transitions to molecular orbitals with 3d<sub>xz</sub>, 3d<sub>yz</sub> and 3d<sub>z2</sub> character, thus accounting for the somewhat higher overall intensity for <b>3</b>.en_US
dc.identifier.citationCao, R., Thomas, K.E., Ghosh, A. & Sarangi, R. (2020). X-ray absorption spectroscopy of archetypal chromium porphyrin and corrole derivatives. <i>RSC Advances, 10</i>, 20572-20578.en_US
dc.identifier.cristinIDFRIDAID 1849648
dc.identifier.doihttps://doi.org/10.1039/D0RA02335C
dc.identifier.issn2046-2069
dc.identifier.urihttps://hdl.handle.net/10037/20524
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.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2020 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 archetypal chromium porphyrin and corrole derivativesen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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