Mass spectrometry, photoelectron spectroscopy, and quantum chemical studies of fluorofullerene dianions

Fullerene “Superhalogen” Radicals: the Substituent Effect on Electronic Properties of 1,7,11,24,27‐C60X5

“…In the earlier theoretical considerations, it was hypothesized that high EA of highly fluorinated fullerene, C 60 F 34 , could be due to the presence of two cyclopentadiene moieties in its structure. [13] In this work, in order to analyze if there is a correlation between the addend X and aromaticity, we have computed nucleus-independent chemical shifts (NICS) at several points of C 60 X 5 À anions, namely at the center of the cyclopentadiene ring, at the center of the opposite cage ring, and the center of C 60 cage. These calculations showed that, as anticipated, the cylopentadiene ring is aromatic with NICS values of À5 to À13 ppm, whereas the opposite pentagon is always antiaromatic (positive NICS values of 10-12 ppm).…”

“…One of the factors resulting in the high electron affinity of C 60 X 5 radicals is the formation of the aromatic cyclopentadiene anion. In the earlier theoretical considerations, it was hypothesized that high EA of highly fluorinated fullerene, C 60 F 34 , could be due to the presence of two cyclopentadiene moieties in its structure 13. In this work, in order to analyze if there is a correlation between the addend X and aromaticity, we have computed nucleus‐independent chemical shifts (NICS) at several points of C 60 X 5 − anions, namely at the center of the cyclopentadiene ring, at the center of the opposite cage ring, and the center of C 60 cage.…”

Evolution of lone pair of excess electrons inside molecular cages with the deformation of the cage in e2@C60F60systems

“…This is in accordance with the order of the total energies of the three isomers. The EDAs of C 60 F 34 2− (2.50 eV39b and 2.40 eV46), C 60 F 46 2− (3.33 eV39b and 3.20 eV46), and C 60 F 48 2− (4.06 eV39) have been reported. The VDE (I) values for the three isomers are larger than those of −0.021 to 1.254 eV for the solvated dielectron clusters e 2 @(LiF) n ( n = 3–5)21 and those of about 1.0 eV24, 27 for the dipole bound dianions of [(PF 5 ) 3 ···dropentalene → Ca] 2− and [(LiCN) n ···LiCC → PF 5 ] 2− .…”

Electron interaction with S6-C60(CF3)12: Energy pool of fullerene cage

“…To rationalize our experimental results, a DFT (PBE/TZ2P) calculation (PRIRODA package [20]) of the orbital energies for the C 60 (CF 3 ) 12 + cation have been carried out. According to the comparison with the ultraviolet (UV) [21] photoelectron and near-edge X-ray absorption fine structure (NEXAFS) spectra, this theoretical methodology provides sufficiently accurate qualitative description of the frontier orbitals in fullerene derivatives. The calculated spectra of the ␣-and ␤-spin orbitals of cation are shown in Fig.…”