title: Persistent oxidation dications from twisted fluoranthenes, benzo[k]fluoranthene and dimethyldibenzo[j.l]fluoranthene: charge delocalization mode, tropicity, and formation of novel 8,8'-bifluoranthenyls. An NMR and theoretical study.
abstract: First examples of persistent oxidation dications from fluoranthene-PAHs namely 1,3,4,6,7,10-hexamethyl- 2 and 3,4-dichloro-1,6,7,10-tetramethylfluoranthene 3, benzo[k]fluoranthene 6, and 3,6-dimethyldibenzo[j,l]fluoranthene 9 are reported. Charge delocalization mode and tropicity in the resulting nonalternant dications are examined. Quenching of the superacid solutions of the dications resulted in the formation of novel 8,8'-bifluoranthenyls 2a-4a. AM1 was used as an initial guide for dication generation (DeltaDeltaH(f) degrees and ionization potentials) and for probing the structures of the crowded fluoranthene substrates and their bifluoranthenyls. In selected cases, the dications and their neutral precursors were calculated at the B3LYP/6-31G(d,p) level. Charge delocalization mode (difference in NPA charges) and DFT/GIAO-derived NMR chemical shifts were obtained for comparison with experiment; aromaticity was assessed via nucleus independent chemical shift (NICS) calculations.
authors.affiliation: Department of Chemistry, Kent State University, Kent, OH 44242, USA. klaali@kent.edu
authors.forename: K K
authors.initials: KK
authors.lastname: Laali
authors.forename: T
authors.initials: T
authors.lastname: Okazaki
authors.forename: S E
authors.initials: SE
authors.lastname: Galembeck
authors.forename: J S
authors.initials: JS
authors.lastname: Siegel
mesh_terms: D005449:Fluorenes / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D010084:Oxidation-Reduction
chemical_list: D005449:Fluorenes