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

Research output: Contribution to journalArticle

71 Citations (Scopus)

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.

LanguageEnglish
Pages6750-6753
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number21
DOIs
Publication statusPublished - 3 Jun 2015

Fingerprint

Pyrene
Electrons
Anions
Negative ions
Boron
Near-Infrared Spectroscopy
X ray crystallography
X Ray Crystallography
Discrete Fourier transforms
Cyclic voltammetry
Paramagnetic resonance
Nuclear magnetic resonance
Spectroscopy
pyrene

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
Ji, Lei ; Edkins, Robert M. ; Lorbach, Andreas ; Krummenacher, Ivo ; Brückner, Charlotte ; Eichhorn, Antonius ; Braunschweig, Holger ; Engels, Bernd ; Low, Paul J. ; Marder, Todd B. / Electron delocalization in reduced forms of 2-(BMes2)pyrene and 2,7-Bis(BMes2)pyrene. In: Journal of the American Chemical Society . 2015 ; Vol. 137, No. 21. pp. 6750-6753.
@article{2844cbd015374636a1a444fb68d9d44e,
title = "Electron delocalization in reduced forms of 2-(BMes2)pyrene and 2,7-Bis(BMes2)pyrene",
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.",
keywords = "electron delocalization, pyrene",
author = "Lei Ji and Edkins, {Robert M.} and Andreas Lorbach and Ivo Krummenacher and Charlotte Br{\"u}ckner and Antonius Eichhorn and Holger Braunschweig and Bernd Engels and Low, {Paul J.} and Marder, {Todd B.}",
year = "2015",
month = "6",
day = "3",
doi = "10.1021/jacs.5b03805",
language = "English",
volume = "137",
pages = "6750--6753",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "21",

}

Ji, L, Edkins, RM, Lorbach, A, Krummenacher, I, Brückner, C, Eichhorn, A, Braunschweig, H, Engels, B, Low, PJ & Marder, TB 2015, 'Electron delocalization in reduced forms of 2-(BMes2)pyrene and 2,7-Bis(BMes2)pyrene' Journal of the American Chemical Society , vol. 137, no. 21, pp. 6750-6753. https://doi.org/10.1021/jacs.5b03805

Electron delocalization in reduced forms of 2-(BMes2)pyrene and 2,7-Bis(BMes2)pyrene. / Ji, Lei; Edkins, Robert M.; Lorbach, Andreas; Krummenacher, Ivo; Brückner, Charlotte; Eichhorn, Antonius; Braunschweig, Holger; Engels, Bernd; Low, Paul J.; Marder, Todd B.

In: Journal of the American Chemical Society , Vol. 137, No. 21, 03.06.2015, p. 6750-6753.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Electron delocalization in reduced forms of 2-(BMes2)pyrene and 2,7-Bis(BMes2)pyrene

AU - Ji, Lei

AU - Edkins, Robert M.

AU - Lorbach, Andreas

AU - Krummenacher, Ivo

AU - Brückner, Charlotte

AU - Eichhorn, Antonius

AU - Braunschweig, Holger

AU - Engels, Bernd

AU - Low, Paul J.

AU - Marder, Todd B.

PY - 2015/6/3

Y1 - 2015/6/3

N2 - 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.

AB - 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.

KW - electron delocalization

KW - pyrene

UR - http://www.scopus.com/inward/record.url?scp=84930659508&partnerID=8YFLogxK

U2 - 10.1021/jacs.5b03805

DO - 10.1021/jacs.5b03805

M3 - Article

VL - 137

SP - 6750

EP - 6753

JO - Journal of the American Chemical Society

T2 - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 21

ER -