title: Perfluorinated polycyclic aromatic hydrocarbons: anthracene, phenanthrene, pyrene, tetracene, chrysene, and triphenylene.
abstract: The properties of perfluoroanthracene (1-C(14)F(10)), perfluorophenanthrene (2-C(14)F(10)), perfluoropyrene (C(16)F(10)), perfluorotetracene (1-C(18)F(12)), perfluorochrysene (2-C(18)F(12)), and perfluorotriphenylene (3-C(18)F(12)) and their radical anions have been studied using density functional theory (DFT). Three measures of neutral-anion energy separations reported in this work are the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA(vert)), and the vertical detachment energy (VDE). The vibrational frequencies of these perfluoro PAHs and their radical anions are also examined. The predicted adiabatic electron affinities (DZP++ B3LYP) are: 1.84 eV, 1-C(14)F(10); 1.41 eV, 2-C(14)F(10); 1.72 eV, C(16)F(10); 2.39 eV, 1-C(18)F(12); 1.83 eV (C(i) symmetry) and 1.88 eV (C(2) symmetry), 2-C(18)F(12); and 1.69 eV, 3-C(18)F(12). The perfluorotetracene is clearly the most effective electron captor. Perfluorophenanthrene, perfluoropyrene, perfluorochrysene, and perfluorotriphenylene, as well as their radical anions deviate from planarity. For example, the nonplanar perfluorochrysene structures are predicted to lie 7-13 kcal/mol below the pertinent C(2h) stationary points.
authors.affiliation: School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China.
authors.forename: Xuejun
authors.initials: X
authors.lastname: Feng
authors.forename: Qianshu
authors.initials: Q
authors.lastname: Li
authors.forename: Jiande
authors.initials: J
authors.lastname: Gu
authors.forename: F Albert
authors.initials: FA
authors.lastname: Cotton
authors.forename: Yaoming
authors.initials: Y
authors.lastname: Xie
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer
mesh_terms: D000873:Anthracenes / Q000737:chemistry; D002911:Chrysenes / Q000737:chemistry; D005466:Fluorocarbons / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009279:Naphthacenes / Q000737:chemistry; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D011721:Pyrenes / Q000737:chemistry
chemical_list: D000873:Anthracenes; D002911:Chrysenes; D005466:Fluorocarbons; D005609:Free Radicals; D009279:Naphthacenes; D011084:Polycyclic Aromatic Hydrocarbons; D011721:Pyrenes; C031180:chrysene; C009590:triphenylene; C030984:pyrene; C034020:anthracene; C487736:naphthacene; C047722:perfluorophenanthrene