Electrosynthesis and characterization of 1,2-dibenzyl C-60: A revisit

A reinvestigation of the reaction between C-60(2-) and benzyl bromide in benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) has shown that there are more reaction products than previously reported. Use of a silica rather than a "Buckyclutcher I" column for HPLC purification led to isolation of two previously unattained products in the reaction mixture, one of which was identified as 1,2-(PhCH2)(2)C-60 by UV-vis and NMR. The earlier incorrectly assigned 1,2-(PhCH2)(2)C-60 was identified as the methanofullerene C61HPh by X-ray single-crystal diffraction. The electrochemistry of genuine 1,2-(PhCH2)(2)C-60 shows that its first reduction potential in PhCN containing 0.1 M TBAP is cathodically shifted by 100 mV with respect to E-1/2 for reduction of 1,4-(PhCH2)(2)C-60, indicating that the addition pattern significantly affects the electrochemistry of derivatized C-60. Visible and near-IR spectra of the monoanion and dianion of 1,2-(PhCH2)(2)C-60 are also reported.

Gas-phase ion-molecule reactions of C-60 and theoretical studies of [C60C2H3O](+) adduct cations

Gas-phase ion-molecule reactions of buckminsterfullerene (C-60) with the acetyl cation CH3-C-+=O (m/z 43) and formylmethyl cation (CH2)-C-+-CH=O (m/z 43, or oxiranyl cation), generated from the self-chemical ionization of acetone and vinyl acetate, respectively, were studied in the ion source of a mass spectrometer. Adduct cations [C60C2H3O](+) (m/z 763) and protonated C-60, [C60H](+) (m/z 721), were observed as the major products. AM1 semiempirical molecular orbital calculations on the possible structures, stabilities and charge locations of the isomers of the adducts [C60C2H3O](+) were carried out at the restricted Hartree-Fock level. The results indicated that the sigma-addition product [C-60-COCH3](+) is the most stable adduct for the reaction of C-60 with CH3-C-+=O rather than that resulting from the [2+2] cycloaddition. The [2+3] cycloadduct and the sigma-adduct [C60CH2CHO](+) might be the most possible coexisting products for the reactions of C-60 with (CH2)-C-+-CH=O or oxiranyl cation. Other [C60C2H3O](+) isomers are also discussed. (C) 1997 by John Wiley & Sons, Ltd.

INVESTIGATION OF C-60 SINGLE-CRYSTAL BY X-RAY-METHODS

C-60 Single crystals grown by a single-temperature-gradient technique were characterized by synchrotron radiation white beam x-ray topography and x-ray double crystal diffraction with Cu K-alpha 1 radiation on conventional x-ray source. The results show that the crystal is rather well crystallized, The x-ray topographies give an evidence of dendritic growth mechanism of C-60 Single crystal, and x-ray double crystal diffraction rocking curve shows that there are mosaic structural defects in the sample. A phase transition st 249+/-1.5% K from a simple cubic to a face centered cubic structure is confirmed by in situ observation of synchrotron radiation white beam x-ray topography with the temperature varing from 230 to 295 K.

重离子~(12)C对~(60)Coγ射线诱发人染色体畸变效应的比较研究

目的　重离子和高剂量率6 0 Coγ射线照射离体人血建立染色体畸变的剂量 效应曲线 ;比较重离子1 2 C照射与6 0 Coγ射线照射诱发染色体畸变的相对生物效能。方法　重离子1 2 C和6 0 Coγ射线照射离体人血 ,吸收剂量率为 3Gy min ,吸收剂量为 1 0～ 8 0Gy。主要记录染色体型畸变的非稳定性畸变 ,对双着丝粒体和着丝粒环做曲线拟合 ,并检验回归系数的显著性和曲线的拟合度。结果　重离子1 2 C和6 0 Coγ射线照射离体血诱发的染色体畸变 (双 +环 ) ,在 0～ 8Gy范围内 ,呈良好的剂量 效应关系。1 2 C离子诱发染色体畸变的RBE值是不恒定的 ,它随吸收剂量增加而减少 ,在 0 3～ 8 0Gy范围内 ,RBE值 (Dγ Dc)从 2 6 2到 1 0 0 ,平均 1 5 8。结论　1 2 C离子对6 0 Coγ射线照射诱发染色体畸变 ,在照射剂量较低时 ,有较高的生物效应。

Kinetic energies of C-n(+) (n <= 58) fragment ions produced by nanosecond laser impact on C-60

Laser-induced fragmentation of C-60 has been studied using a time-of-flight mass spectrometric technique. The average kinetic energies of fragment ions C-n(+) (n <= 58) have been extracted from the measured full width at half maximum (FWHM) of ion beam profiles. The primary formation mechanism of small fragment ion C-n(+) (n < 30) is assumed to be a two-step fragmentation process: C60 sequential decay to unstable C-30(+) ion and the binary fission of C-30(+). Considering a second photo absorption process in the later part of laser pulse duration, good agreement is achieved between experiment and theoretical description of photoion formation. (C) 2009 Elsevier B. V. All rights reserved.

Molecular vibration spectroscopy study of irradiation effect in C-60 films induced by low energy ion

Irradiation effect in C-60 films induced by 170 keV B ion was investigated by means of Fourier transform infrared (FTIR) and Raman spectroscopies. The damage cross section sigma and the effective damage radius R are deduced from the experimental data of all four IR active modes and evident four Raman active modes of C-60 molecule. The differences on irradiation sensitivity and structural stability of the different active modes of C-60 molecule are compared. The results indicate that T-1u (4) of infrared active mode and A(g) (1) of Raman active mode are most sensitive for B ion irradiation. On the other hand T-1u (2) of infrared active mode and H-g (3) of Raman active mode are comparatively stable under B ion irradiation. (C) 2010 American Institute of Physics. [doi:10.1063/1.3512968]

Structural stability of C-60 films under the bombardment of 1.95 GeV Kr ions

The structural stability of C-60 films under the bombardment of 1.95 GeV Kr ions is investigated. The irradiated C-60 films were analyzed by Fourier Transform Infrared (FTIR) spectroscopy and Raman scattering technique. The analytical results indicate that the irradiation induced a decrease of icosahedral symmetry of C-60 molecule and damage of C-60 films; different vibration modes of C-60 molecule have different irradiation sensitivities; the mean efficient damage radius obtained from experimental data is about 1.47 nm, which is in good agreement with thermal spike model prediction.

Synthesis and identification of Heterocyclic derivatives of fullerene C-60: Unexpected reaction of anionic C-60 with benzonitrile

During the reaction of reduced C-60 with benzyl bromide in benzonitrile, a novel cis-1 C-60 adduct, 1,4-dibenzyl-2,3-cyclic phenylimidate C-60 (1), Was obtained rather than the expected product of 1,4-dibenzyl C-60. The structure of compound 1 was analyzed by X-ray single-crystal diffraction, identifying the presence of a five-membered heterocycle at a [5,6] bond of C-60. One of the heteroatoms is assigned as a nitrogen atom; however, the identity of the other heteroatom cannot be determined unambiguously by crystallography due to similarity between the nitrogen and oxygen atoms.