Preparation, crystallographic characterization and theoretical study of two isomers of C70(CF3)12

Ignat'eva, Daria V.; Goryunkov, Alexey A.; Tamm, Nadezhda B.; Ioffe, Ilya N.; Avdoshenko, Stanislav M.; Sidorov, Lev N.; Dimitrov, Anton; Kemnitz, Erhard; Troyanov, Sergey I.

doi:10.1039/b518422c

Cited by 44 publications

(33 citation statements)

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“…The best fit to the experimental spectrum was obtained when the values for these atoms were fixed at 3.37, À3.30, 2.70, 2.40, and À2.28 G, respectively. Note that all DFT-predicted 13 C splitting constants are larger than the experimental ones, but this overestimation is fairly systematic and scaling by a uniform multiplicative factor of 0.85 resulted in close agreement between theory and experiment.…”

Section: Esr Spectroelectrochemical Study Of C 70 a C H T U N G T R Esupporting

confidence: 59%

“…The EPR spectra of the C 70 (R f ) 2 radicalanions exhibited a hyperfine splitting caused by the fluorine atoms. Due to the small linewidth, a rich 13 C satellite structure was also observed in the spectrum of C 70 A C H T U N G T R E N N U N G (CF 3 ) 2 . DFT computations provide good agreement with the experimental a(F) and aA C H T U N G T R E N N U N G ( 13 C) values, thus proving the reliability of the theoretically predicted spin-density distribution in the studied molecules.…”

Section: Discussionmentioning

confidence: 95%

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ESR‐Vis/NIR Spectroelectrochemical Study of C₇₀(CF₃)₂^−. and C₇₀(C₂F₅)₂^−. Radical Anions

et al. 2008

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A spectroelectrochemical study of the two isostructural asymmetric perfluoroalkyl derivatives C(1)-7,24-C(70)(CF(3))(2) and C(1)-7,24-C(70)(C(2)F(5))(2) is presented. Reversible formation of their stable monoanion radicals is monitored by cyclic voltammetry and by in situ ESR-Vis-NIR spectroelectrochemistry. The ESR spectrum of the C(70)(CF(3))(2) (-*) radical is a 1:3:3:1 quartet with a (19)F hyperfine coupling constant (a(F)) of 0.323(4) G, demonstrating that the unpaired spin is coupled to only one of the two CF(3) groups. The (13)C satellites are assigned to specific carbon atoms. The ESR spectrum of the C(70)(C(2)F(5))(2) (-*) radical is an apparent octet with an apparent a(F) value of 0.83(2) G. DFT calculations suggest that this pattern is due to the superposition of spectra for four nearly isoenergetic C(70)(C(2)F(5))(2) (-*) conformers. Time-dependent DFT calculations suggest that the NIR band at 1090 nm exhibited by both C(70)(R(f))(2) (-*) radical anions is assigned to the SOMO-->LUMO+3 transition. The analogous NIR band exhibited by the closed-shell C(70)(CF(3))(2) (2-) dianion was blue-shifted to 1000 nm.

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Section: Esr Spectroelectrochemical Study Of C 70 a C H T U N G T R Esupporting

confidence: 59%

Section: Discussionmentioning

confidence: 95%

ESR‐Vis/NIR Spectroelectrochemical Study of C₇₀(CF₃)₂^−. and C₇₀(C₂F₅)₂^−. Radical Anions

et al. 2008

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“…5 atm in a sealed glass ampoule at 440°C is used for the high-yielding preparation of higher polytrifluoromethyl derivatives, C 60/70 (CF 3 ) n (n = 12, 14, 16, 18). [13,14,22,30,31] The trifluoromethylation of fullerenes with CF 3 COOAg was carried out by the Sussex University and Moscow State University research groups, although their approaches were slightly different. In the work published in refs.…”

Section: Synthesismentioning

confidence: 99%

Synthesis, Structure, and Theoretical Study of Lower Trifluoromethyl Derivatives of [60]Fullerene

et al. 2007

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A number of C60(CF3)n compounds with n = 2–10 have been synthesized by the reaction of C60 with silver trifluoroacetate and successfully isolated by means of HPLC. This resulted in the first crystal structure determination of six lower trifluoromethyl derivatives with n = 2 (single isomer), 4 (two isomers), and 6 (three isomers). A kinetic model of sequential trifluoromethylation based on the Bell–Evans–Polanyi principle has been used to explain the experimentally observed isomeric distribution in the mixtures of C60(CF3)n compounds up ton = 6. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…At present, experimentally determined addition patterns (locations of attached groups) on the С 70 fullerene sphere are known for 30 C 70 (CF 3 ) n isomers (n = [6][7][8][9][10][11][12][13][14][15][16][17][18]. The total number of theoretically possible isomers is of the order of tens and hundreds thousands.…”

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New C70(CF3) n isomers (n = 12, 14, 16). Realkylation and addend rearrangements

et al. 2009

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New isomers of trifluoromethyl derivatives of [70]fullerene, C 70 (CF 3 ) 12 (one isomer), C 70 (CF 3 ) 14 (three isomers), and C 70 (CF 3 ) 16 (one isomer) were synthesized, chromatographi cally isolated, and characterized by single crystal X ray analysis. Three of the five new isomers were obtained by annealing a mixture of higher trifluoromethyl derivatives (realkylation*). Trifluoromethylation of two individual C 70 (CF 3 ) 12 isomers revealed rearrangements of CF 3 groups on the fullerene sphere along with the direct addition to the double bonds. The relative energies of the isomers were calculated using the density functional theory.

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Preparation, crystallographic characterization and theoretical study of two isomers of C70(CF3)12

Abstract: Two isomers of C70(CF3)12 have been isolated from a mixture obtained by trifluoromethylation of C70 with CF3I; their molecular structures determined by X-ray crystallography are in good agreement with the results of theoretical DFT calculations for the most stable C70(CF3)12 isomers.

Cited by 44 publications

References 17 publications

ESR‐Vis/NIR Spectroelectrochemical Study of C₇₀(CF₃)₂^−. and C₇₀(C₂F₅)₂^−. Radical Anions

ESR‐Vis/NIR Spectroelectrochemical Study of C₇₀(CF₃)₂^−. and C₇₀(C₂F₅)₂^−. Radical Anions

Synthesis, Structure, and Theoretical Study of Lower Trifluoromethyl Derivatives of [60]Fullerene

New C70(CF3) n isomers (n = 12, 14, 16). Realkylation and addend rearrangements

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Preparation, crystallographic characterization and theoretical study of two isomers of C70(CF3)12

Abstract: Two isomers of C70(CF3)12 have been isolated from a mixture obtained by trifluoromethylation of C70 with CF3I; their molecular structures determined by X-ray crystallography are in good agreement with the results of theoretical DFT calculations for the most stable C70(CF3)12 isomers.

Cited by 44 publications

References 17 publications

ESR‐Vis/NIR Spectroelectrochemical Study of C70(CF3)2−. and C70(C2F5)2−. Radical Anions

ESR‐Vis/NIR Spectroelectrochemical Study of C70(CF3)2−. and C70(C2F5)2−. Radical Anions

Synthesis, Structure, and Theoretical Study of Lower Trifluoromethyl Derivatives of [60]Fullerene

New C70(CF3) n isomers (n = 12, 14, 16). Realkylation and addend rearrangements

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ESR‐Vis/NIR Spectroelectrochemical Study of C₇₀(CF₃)₂^−. and C₇₀(C₂F₅)₂^−. Radical Anions

ESR‐Vis/NIR Spectroelectrochemical Study of C₇₀(CF₃)₂^−. and C₇₀(C₂F₅)₂^−. Radical Anions