Electron delocalization in reduced forms of 2-(BMes2)pyrene and 2,7-Bis(BMes2)pyrene

Lei Ji, Robert M. Edkins, Andreas Lorbach, Ivo Krummenacher, Charlotte Brückner, Antonius Eichhorn, Holger Braunschweig, Bernd Engels, Paul J. Low, Todd B. Marder

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Abstract

Reduction of 2-(BMes2)pyrene (B1) and 2,7-bis(BMes2)pyrene (B2) gives rise to anions with extensive delocalization over the pyrenylene bridge and between the boron centers at the 2- and 2,7-positions, the typically unconjugated sites in the pyrene framework. One-electron reduction of B2 gives a radical anion with a centrosymmetric semiquinoidal structure, while two-electron reduction produces a quinoidal singlet dianion with biradicaloid character and a relatively large S0-T1 gap. These results have been confirmed by cyclic voltammetry, X-ray crystallography, DFT/CASSCF calculations, NMR, EPR, and UV-vis-NIR spectroscopy.

Original languageEnglish
Pages (from-to)6750-6753
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number21
Early online date22 May 2015
DOIs
Publication statusPublished - 3 Jun 2015

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Keywords

  • electron delocalization
  • pyrene

Cite this

Ji, L., Edkins, R. M., Lorbach, A., Krummenacher, I., Brückner, C., Eichhorn, A., ... Marder, T. B. (2015). Electron delocalization in reduced forms of 2-(BMes2)pyrene and 2,7-Bis(BMes2)pyrene. Journal of the American Chemical Society , 137(21), 6750-6753. https://doi.org/10.1021/jacs.5b03805