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Article: Structural, optical, and electrochemical properties of three-dimensional push-pull corannulenes

TitleStructural, optical, and electrochemical properties of three-dimensional push-pull corannulenes
Authors
Issue Date2012
Citation
Journal of Organic Chemistry, 2012, v. 77, n. 24, p. 11014-11026 How to Cite?
AbstractElectrochemically active corannulene derivatives with various numbers of electron-donating 4-(N,N-dimethylamino)phenylethynyl (1-4) or electron-withdrawing cyanobutadienyl peripheral substitutents (5-8) were prepared. The latter derivatives resulted from formal [2 + 2] cycloaddition of cyanoolefins to 1-4 followed by retro-electrocyclization. Conformational properties were examined by variable-temperature NMR and X-ray diffraction and opto-electronic properties by electronic absorption/emission spectra and electrochemical measurements; these analyses were corroborated by dispersion-corrected density functional calculations at the level of B97-D/def2-TZVPP. In CH2Cl2, 1-4 exhibit intramolecular charge-transfer (ICT) absorptions at 350-550 nm and green (λem ∼ 540 nm) or orange (600 nm) fluorescence with high quantum yields (56-98%) and are more readily reduced than corannulene by up to 490 mV. The variation of optical gap and redox potentials of 1-4 does not correlate with the number of substituents. Cyanobutadienyl corannulenes 5-8 show red-shifted ICT absorptions with end-absorptions approaching 800 nm. Intersubstituent interactions lead to distortions of the corannulene core and lower the molecular symmetry. NMR, X-ray, and computational studies on 5 and 8 with one cyanobutadienyl substituent suggested the formation of intermolecular corannulene dimers. Bowl-inversion barriers around ΔG† = 10-11 kcal/mol were determined for these two molecules. © 2012 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/341132
ISSN
2023 Impact Factor: 3.3
2023 SCImago Journal Rankings: 0.724
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWu, Yi Lin-
dc.contributor.authorStuparu, Mihaiela C.-
dc.contributor.authorBoudon, Corinne-
dc.contributor.authorGisselbrecht, Jean Paul-
dc.contributor.authorSchweizer, W. Bernd-
dc.contributor.authorBaldridge, Kim K.-
dc.contributor.authorSiegel, Jay S.-
dc.contributor.authorDiederich, François-
dc.date.accessioned2024-03-13T08:40:25Z-
dc.date.available2024-03-13T08:40:25Z-
dc.date.issued2012-
dc.identifier.citationJournal of Organic Chemistry, 2012, v. 77, n. 24, p. 11014-11026-
dc.identifier.issn0022-3263-
dc.identifier.urihttp://hdl.handle.net/10722/341132-
dc.description.abstractElectrochemically active corannulene derivatives with various numbers of electron-donating 4-(N,N-dimethylamino)phenylethynyl (1-4) or electron-withdrawing cyanobutadienyl peripheral substitutents (5-8) were prepared. The latter derivatives resulted from formal [2 + 2] cycloaddition of cyanoolefins to 1-4 followed by retro-electrocyclization. Conformational properties were examined by variable-temperature NMR and X-ray diffraction and opto-electronic properties by electronic absorption/emission spectra and electrochemical measurements; these analyses were corroborated by dispersion-corrected density functional calculations at the level of B97-D/def2-TZVPP. In CH2Cl2, 1-4 exhibit intramolecular charge-transfer (ICT) absorptions at 350-550 nm and green (λem ∼ 540 nm) or orange (600 nm) fluorescence with high quantum yields (56-98%) and are more readily reduced than corannulene by up to 490 mV. The variation of optical gap and redox potentials of 1-4 does not correlate with the number of substituents. Cyanobutadienyl corannulenes 5-8 show red-shifted ICT absorptions with end-absorptions approaching 800 nm. Intersubstituent interactions lead to distortions of the corannulene core and lower the molecular symmetry. NMR, X-ray, and computational studies on 5 and 8 with one cyanobutadienyl substituent suggested the formation of intermolecular corannulene dimers. Bowl-inversion barriers around ΔG† = 10-11 kcal/mol were determined for these two molecules. © 2012 American Chemical Society.-
dc.languageeng-
dc.relation.ispartofJournal of Organic Chemistry-
dc.titleStructural, optical, and electrochemical properties of three-dimensional push-pull corannulenes-
dc.typeArticle-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jo302217n-
dc.identifier.scopuseid_2-s2.0-84871595266-
dc.identifier.volume77-
dc.identifier.issue24-
dc.identifier.spage11014-
dc.identifier.epage11026-
dc.identifier.eissn1520-6904-
dc.identifier.isiWOS:000312564900002-

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