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dc.contributor.authorGhosh, Abhik
dc.contributor.authorConradie, Jeanet
dc.date.accessioned2021-12-07T14:50:39Z
dc.date.available2021-12-07T14:50:39Z
dc.date.issued2021-11-11
dc.description.abstractNearly a half-century after Gouterman classified the UV–vis–NIR spectra of porphyrin derivatives as normal, hyper, or hypso, we propose a heretofore unsuspected “mechanism” underlying hypso spectra. Hypsoporphyrins, which exhibit blueshifted optical spectra relative to normal porphyrins (such as Zn porphyrins), typically involve dn transition metal ions, where n > 6. The spectral blueshifts have been traditionally ascribed to elevated porphyrin eg LUMO (lowest unoccupied molecular orbital) energy levels as a result of antibonding interactions with metal dπ orbitals. Herein, we have found instead that the blueshifts reflect a lowering of the a<sub>2u</sub> HOMO (highest occupied molecular orbital) energy levels. Electronegative metals such as Pd and Pt transfer smaller quantities of electron density to the porphyrin nitrogens, compared to a more electropositive metal such as Zn. With large amplitudes at the porphyrin nitrogens, the a<sub>2u</sub> HOMOs of Pd(II) and Pt(II) porphyrins accordingly exhibit lower orbital energies than those of Zn(II) porphyrins, thus explaining the hypso effect. Hypso spectra are also observed for corroles: compared with six-coordinate Al(III) corroles, which may be thought of exhibiting normal spectra, Au(III) corroles, for instance, exhibit blueshifted or hypso spectra.en_US
dc.identifier.citationGhosh, Conradie. The Dog That Didn't Bark: A New Interpretation of Hypsoporphyrin Spectra and the Question of Hypsocorroles. Journal of Physical Chemistry A. 2021en_US
dc.identifier.cristinIDFRIDAID 1963859
dc.identifier.doi10.1021/acs.jpca.1c08425
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.urihttps://hdl.handle.net/10037/23313
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalJournal of Physical Chemistry A
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.titleThe Dog That Didn't Bark: A New Interpretation of Hypsoporphyrin Spectra and the Question of Hypsocorrolesen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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