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dc.contributor.authorThomas, Kolle E.
dc.contributor.authorSlebodnick, Carla
dc.contributor.authorGhosh, Abhik
dc.date.accessioned2021-02-08T10:02:22Z
dc.date.available2021-02-08T10:02:22Z
dc.date.issued2020-04-02
dc.description.abstractA porphyrin cis tautomer, where the two central NH protons are on adjacent pyrrole rings, has long been invoked as an intermediate in porphyrin tautomerism. Only recently, however, has such a species been isolated and structurally characterized. Thus, single-crystal X-ray structure determinations of two highly saddled free-base porphyrins, β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H<sub>2</sub>[(CF<sub>3</sub>)<sub>7</sub>TFPP], and β-octaiodo-5,10,15,20-tetrakis(4′-trifluoromethylphenyl)porphyrin, H<sub>2</sub>[I<sub>8</sub>TCF<sub>3</sub>PP], unambiguously revealed cis tautomeric structures, each stabilized as a termolecular complex with a pair of ROH (R = CH<sub>3</sub> or H) molecules that form hydrogen-bonded N–H···O–H···N straps connecting the central NH groups with the antipodal unprotonated nitrogens. The unusual substitution patterns of these two porphyrins, however, have left open the question how readily such supramolecular assemblies might be engineered, which prompted us to examine the much more synthetically accessible β-octabromo-meso-tetraphenylporphyrins. Herein, single-crystal X-ray structures were obtained for two such compounds, 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4′-trifluoromethylphenyl)porphyrin, H<sub>2</sub>[Br<sub>8</sub>TCF<sub>3</sub>PP], and 2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(4′-fluorophenyl)porphyrin, H<sub>2</sub>[Br<sub>8</sub>TFPP], and although the central hydrogens could not all be located unambiguously, the electron density could be convincingly modeled as porphyrin cis tautomers, existing in each case as a bis-methanol adduct. In addition, a perusal of the Cambridge Structural Database suggests that there may well be additional examples of porphyrin cis tautomers that have not been recognized as such. We are therefore increasingly confident that porphyrin cis tautomers are readily accessible via supramolecular engineering, involving the simple stratagem of crystallizing a strongly saddled porphyrin from a solvent system containing an amphiprotic species such as water or an alcohol.en_US
dc.identifier.citationThomas, K.E., Slebodnick, C. & Ghosh, A. (2020). Facile Supramolecular Engineering of Porphyrin cis Tautomers: The Case of β-Octabromo-meso-tetraarylporphyrins. <i>ACS Omega, 5</i>(15), 8893-8901.en_US
dc.identifier.cristinIDFRIDAID 1849632
dc.identifier.doihttps://doi.org/10.1021/acsomega.0c00517
dc.identifier.issn2470-1343
dc.identifier.urihttps://hdl.handle.net/10037/20528
dc.language.isoengen_US
dc.publisherACS Publicationsen_US
dc.relation.journalACS Omega
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.titleFacile Supramolecular Engineering of Porphyrin cis Tautomers: The Case of β-Octabromo-meso-tetraarylporphyrinsen_US
dc.type.versionpublishedVersionen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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