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dc.contributor.authorWamser, Carl C.
dc.contributor.authorGhosh, Abhik
dc.date.accessioned2023-01-17T11:39:22Z
dc.date.available2023-01-17T11:39:22Z
dc.date.issued2022-06-30
dc.description.abstractThe Gouterman four-orbital model conceptualizes porphyrin UV−visible spectra as dominated by four frontier molecular orbitals-two nearly degenerate HOMOs and two exactly degenerate LUMOS under D<sub>4h</sub> symmetry. These are well separated from all the other molecular orbitals, and normal spectra involve transitions among these MOs. Unusual spectra occur when additional orbitals appear in this energy range, typically as a consequence of the central coordinated atom. For example, metals with empty d orbitals in a suitable energy range may lead to charge transfer from porphyrin (ligand) to metal, that is, so-called LMCT transitions. Metals with filled p or d orbitals may lead to charge transfer from metal to porphyrin, MLCT transitions. These cases lead to additional peaks and/or significant redshifts in the spectra and were classified as hyperporphyrins by Gouterman. Cases in which spectra are blueshifted were classified as hypsoporphyrins; they are common for relatively electronegative late transition metal porphyrins. Many of the same principles apply to porphyrin analogues, especially corroles. In this Perspective, we focus on two newer classes of hyperporphyrins: one reflecting substituent effects in protonated or deprotonated free-base tetraphenyporphyrins and the other reflecting “noninnocent” interactions between central metal ions and corroles. Hyperporphyrin effects on spectra can be dramatic, yet they can be generated by relatively simple changes and subtle structural variations, such as acid−base reactions or the selection of a central metal ion. These concepts suggest strategies for engineering porphyrin or porphyrinoid dyes for specific applications, especially those requiring far-red or near-infrared absorption or emission.en_US
dc.identifier.citationWamser, Ghosh. The Hyperporphyrin Concept: A Contemporary Perspective. Journal of the American Chemical Society. 2022;2(7):1543-1560en_US
dc.identifier.cristinIDFRIDAID 2097926
dc.identifier.doi10.1021/jacsau.2c00255
dc.identifier.issn0002-7863
dc.identifier.issn1520-5126
dc.identifier.urihttps://hdl.handle.net/10037/28275
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalJournal of the American Chemical Society
dc.rights.accessRightsopenAccessen_US
dc.rights.holderCopyright 2022 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.titleThe Hyperporphyrin Concept: A Contemporary Perspectiveen_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)