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.
authors.affiliation: †Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Lei
authors.initials: L
authors.lastname: Ji
authors.affiliation: †Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Robert M
authors.initials: RM
authors.lastname: Edkins
authors.affiliation: †Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Lorbach
authors.affiliation: †Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Ivo
authors.initials: I
authors.lastname: Krummenacher
authors.affiliation: ‡Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Emil-Fischer-Straße 42, 97074 Würzburg, Germany.
authors.forename: Charlotte
authors.initials: C
authors.lastname: Brückner
authors.affiliation: †Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Antonius
authors.initials: A
authors.lastname: Eichhorn
authors.affiliation: †Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Holger
authors.initials: H
authors.lastname: Braunschweig
authors.affiliation: ‡Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Emil-Fischer-Straße 42, 97074 Würzburg, Germany.
authors.forename: Bernd
authors.initials: B
authors.lastname: Engels
authors.affiliation: §School of Chemistry and Biochemistry, University of Western Australia, 35 Stirling Highway, Crawley, WA 6009, Australia.
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Low
authors.affiliation: †Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
authors.forename: Todd B
authors.initials: TB
authors.lastname: Marder