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dc.contributor.authorGhosh, Abhik
dc.contributor.authorConradie, Jeanet
dc.date.accessioned2024-09-03T07:38:41Z
dc.date.available2024-09-03T07:38:41Z
dc.date.issued2024-01-23
dc.description.abstractRelativistic DFT (OLYP-D3/ZORA-STO-TZ2P) calculations predict low adiabatic ionization potentials for gold(II) porphyrins, from 4.60 eV for Au[TPP] (TPP = tetraphenylporphyrin) to 5.34 eV for Au[TPFPP] [TPFPP = tetrakis(pentafluorophenyl)porphyrin]. These values are over 1 eV lower than those calculated for analogous silver(II) porphyrins, reflecting much greater relativistic destabilization of the Au 5d orbitals relative to Ag 4d orbitals. Interestingly, our calculations also place the observed structural distortion of Au[TPP] in an entirely new light. The electronic imperative of the Au(II) center to assume a pseudo-d<sup>10</sup> configuration drives a wave deformation of the porphyrin core that allows for Au(d<sub>x</sub> 2-<sub>y</sub> 2 )–porphyrin(π) mixing. The lateral compression–elongation of the porphyrin (unequal pairs of Au–N bonds), in contrast, appears to be a secondary effect, a consequence of the wave deformation. The wave distortion results in significant π spin populations on the porphyrin macrocycle, leaving behind only about 20–25% of the spin density on the gold. The effect is specific to gold: silver(II) porphyrins exhibit strictly planar cores with approximate D4h local symmetry at the metal.en_US
dc.identifier.citationGhosh, Conradie. Rethinking gold(II) porphyrins: an inherent wave distortion. Comptes rendus. Chimie. 2024;27en_US
dc.identifier.cristinIDFRIDAID 2245417
dc.identifier.doi10.5802/crchim.264
dc.identifier.issn1631-0748
dc.identifier.issn1878-1543
dc.identifier.urihttps://hdl.handle.net/10037/34503
dc.language.isoengen_US
dc.publisherAcadémie des Sciencesen_US
dc.relation.journalComptes rendus. Chimie
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2024 The Author(s)en_US
dc.rights.urihttps://creativecommons.org/licenses/by/4.0en_US
dc.rightsAttribution 4.0 International (CC BY 4.0)en_US
dc.titleRethinking gold(II) porphyrins: an inherent wave distortionen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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Attribution 4.0 International (CC BY 4.0)
Med mindre det står noe annet, er denne innførselens lisens beskrevet som Attribution 4.0 International (CC BY 4.0)