title: Electrochemical, ESR and theoretical studies of [6,6]-opened C(60)(CF(2)), cis-2-C(60)(CF(2))(2) and their anions.
abstract: Electrochemical behavior of C(60)(CF(2))(n), n = 1, 2 and C(60)(CCl(2)) has been investigated. [6,6]-Opened C(60)(CF(2)) and cis-2-C(60)(CF(2))(2) exhibit reversible reductions at potentials 150 and 145 mV more positive than C(60), unlike the related [6,6]-closed C(60)(CCl(2)), which shows reduction at the potential close to that for C(60). The structures, electron localization and lifetimes of the observed radical anions C(60)(CF(2))(-*) and cis-2-C(60)(CF(2))(2)(-*) have been elucidated by the ESR study and DFT calculations. The protonation pathway of decay of C(60)(CF(2))(-*) yields [6,6]-opened 1,9-dihydro-(1a,1a-difluoro-1aH-1(9)a-homo(C(60)-I(h))fullerene, C(60)(CF(2))H(2), which becomes the first characterized derivative of [6,6]-opened C(60)(CF(2)). DFT calculations of the structure and electron affinity of a number of homofullerene structures have been carried out to rationalize the experimental findings.
authors.affiliation: Chemistry Department, Moscow State University, Leninskie Gory, Moscow, Russia. aag@thermo.chem.msu.ru
authors.forename: Alexey A
authors.initials: AA
authors.lastname: Goryunkov
authors.forename: Eugenia S
authors.initials: ES
authors.lastname: Kornienko
authors.forename: Tatyana V
authors.initials: TV
authors.lastname: Magdesieva
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Kozlov
authors.forename: Vsevolod A
authors.initials: VA
authors.lastname: Vorobiev
authors.forename: Stanislav M
authors.initials: SM
authors.lastname: Avdoshenko
authors.forename: Ilya N
authors.initials: IN
authors.lastname: Ioffe
authors.forename: Oleg M
authors.initials: OM
authors.lastname: Nikitin
authors.forename: Vitality Yu
authors.initials: VY
authors.lastname: Markov
authors.forename: Pavel A
authors.initials: PA
authors.lastname: Khavrel
authors.forename: Andrey Kh
authors.initials: AKh
authors.lastname: Vorobiev
authors.forename: Lev N
authors.initials: LN
authors.lastname: Sidorov
mesh_terms: D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D037741:Fullerenes / Q000737:chemistry*; D010084:Oxidation-Reduction; D011522:Protons; D011789:Quantum Theory; D013237:Stereoisomerism
chemical_list: D037741:Fullerenes; D011522:Protons; C069837:fullerene C60