Details

Autor(en) / Beteiligte

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

Titel

Electron Delocalization in Reduced Forms of 2‑(BMes2)pyrene and 2,7-Bis(BMes2)pyrene

Ist Teil von

• Journal of the American Chemical Society, 2015-06, Vol.137 (21), p.6750-6753

Ort / Verlag

United States: American Chemical Society

Erscheinungsjahr

2015

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Reduction of 2-(BMes2)­pyrene (B 1 ) and 2,7-bis­(BMes2)­pyrene (B 2 ) 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 B 2 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.