Controllable Synthesis And Characterization Of [60] Fulleropyrrolidine Derivatives Micro/nano Structures

The studies on synthesis and properties of C₆₀-based nanosized materials have been an active topic in the fullerene chemistry. Fabrication of functional fulleropyrrolidine derivatives micro/nano structures, optimizing synthesis condition, studying their photophysical and photochemical properties and exploring novel fullerene-based materials are remarkably meaningful. The thesis is focused on fabrication of [60]fulleropyrrolidine derivatives micro/nano materials by decreasing their solubility, studying the effects of solvents, concentration, surfactant kinds and concentration, temperature and substitute group on C₆₀ on crystal morphology. Fabrication of functional dissymmetric fulleropyrrolidine derivatives micro/nano structures, study their photoelectronic properties will accumulate the date to synthesize novel photoelectronic materials, and will play an important role in exploring new fullerenes-base materials and developing fullerene chemistry. The thesis consists of two aspects as follows:1. N-methyl-2-[4-dimethyl-amido]phenyl-3,4-fulleropyrrolidine was synthesized by 1,3-dipolar cycloaddition reaction, different morphologies of nanostructures were fabricated for the first time using the surfactant assisted self-assembly method. The crystalline structure was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), Raman spectroscopy (Raman) and Photoluminescence (PL) spectroscopy. N-methyl-2-[4-dimethyl-amido]phenyl-3,4-fulleropyrrolidine with anomalistic flakes and regular blooming peonies were obtained and controlled by using different solvents, concentration, surfactant, temperature, and volume ratio of toluene and isopropanol. It is demonstrated that surfactant molecules can assist the crystallization process of the fulleropyrrolidine derivatives. PL spectra and Thermal gravimetric analysis (TGA) showed that the flakes and flowers have narrow PL peak widths and lower intensity than that of powder, which is likely caused by the solvents quenching. These results are remarkably meaningful for studying the controllable fabrication and property of fulleropyrrolidine derivatives micro/nano structures.2. N-methyl-2-pentafluorophenyl-3,4-fulleropyrrolidine, N-methyl- 3,4-fulleropyrrolidine and N-methyl-2-phenyl-3,4-fulleropyrrolidine were synthesized by 1,3-dipolar cycloaddition reaction, their nanostructures with different morphologies were fabricated for the first time using the surfactant assisted self-assembly. The crystal formation, crystalline structure and morphology can be controlled by using different solvents, concentration, surfactant and volume ratio of solvents. N-methyl-2-pentafluorophenyl-3,4-fulleropyrrolidine crystalline structures with morphology of anomalistic grains and flakes, N-methyl-3,4-fulleropyrrolidine crystalline structures with morphology of different size grains, and nomalistic grains, flakes and regular needle-like structures of N-methyl-2-phenyl-3,4-fulleropyrrolidine were obtained. Their crystalline structures and morphologies can be controlled by using different kinds of solvents, surfactant, and different concentrations, volume ratios. When toluene was used as solvent, the crystalline structure and morphology can be well controlled, but not CCl4 do. The appropriate concentration and volume ratio of solvents were important for the crystalline structure and morphology, which is possibly related to the ability of the isopropanol and toluene to intermix and thus have similar polarities, resulted in that the crystal grows more slowly and there is a ripen process. This method supplies controllable preparation of C₆₀-based micro/nano materials.