Study On Fluorination And Trifluomethylation Of [60] Fullerenes

The studies on the synthesis and properties of fluorinated fullerenes have been one of the active topics in the fullerene chemistry. So synthesizing novel fluorinated fullerenes by radical reaction, searching reaction rules, studying their photoelectric properties and exploring fullerene-based new materials are remarkably meaningful, which will play an important role in developing the fullerene chemistry. This thesis is focused on fluorinated and perfluoroalkylated fullerenes formed by radical addition reaction of the fullerene spheroid possessed unique structures and properties, which will accumulate foundation for the design of novel promising materials based on fullerenes.1. A set of equipment to synthesize fluorinated [60]Fullerenes has been set up. A series of fluorinated [60] Fullerenes were obtained by reaction of KF and MnF₃ with C₆₀, isolated and purified by high performance liquid chromatography (HPLC). The main fluorinated [60] fullerenes were characterized by Infrared (IR) spectroscopy and fluorine nuclear magnetic resonance (¹⁹F NMR). The results indicated that the ratio of C₆₀F₁₈ was primarily affected by the reaction temperature, the vacuum degree of reaction and the molar ratios of the reactants.2. The effects of the mole ratios of the reactants and the reaction temperature on the product components of the reaction between [60] fullerenes and CF₃CO₂Ag at high temperature were investigated. After being separated by HPLC, the products were characterized by IR, UV-Vis spectroscopy and ¹⁹F NMR. The experimental results indicated that, the lower the CF₃CO₂Ag/C₆₀ mole ratio (10:1) is, the less CF₃ groups were added to C₆₀ and the less components of the products were obtained with remaining a large amount of unreacted C₆₀; the higher the CF₃CO₂Ag/C₆₀ mole ratio (30:1) is, the more CF₃ groups were added to C₆₀ on average and the more components were obtained. When the mole ratio of reactants (CF₃CO₂Ag/C₆₀) is 20:1, the higher temperature of the reaction is, the more product components were obtained.3. The reactions of N-methyl-2-phenyl-3,4-fulleropyrrolidine and N-methyl -2-pentafluorophenyl-3,4-fulleropyrrolidine with CF₃CO₂Ag at high temperature, respectively, have been studied. The products were isolated and purified by HPLC and characterized by UV-Vis, fluorescence spectrum (FL), IR, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The results indicated the two, four and six of·CF₃ groups have been added to the fullerene spheroid of fullerene pyrrolidines, respectively. However the structures of the products and the accurate positions of·CF₃ also rely on further research. The perfluoroalkylation of [60]Fullerene derivatives is an undeveloped research field. Study on the trifluoromethylated [60] Fullerene derivatives will be greatly significant for further synthesis of novel functional [60]Fullerenes derivatives.