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
SN - 0002-7863
VL - 137
SP - 6750
EP - 6753
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 21
ER -
