Synthesis, Isolation And Properties Of Titanium-based Novel Endohedral Fullerenes

Endohedral fullerenes represent the novel form of fullerenes with atoms, ions, orclusters trapped in their inner space. Mixed metal nitride clusterfullerenes (MMNCFs)is a special family of endohedral fullerenes which encage a nitride cluster comprisingof two to three different metal atoms. Because two to three different metal atoms withdifferent physical properties can be encapsulated within MMNCFs with variablecompositions, the formed MMNCFs may achieve the superior property as thecombination of their different properties, and hence become the multifunctionalmolecular materials. In this dissertation, we synthesized and isolated two new types ofnovel Ti-based MMNCFs (TiSc2N@C80, TiY2N@C80) as well as a novel endohedralmetalloazafullerene (Y@C83N), and have carried out the following works:1. For the first time we encapsulated a non-group-III metal into a metal nitrideclusterfullerene via the DC-arc discharging method—TiSc2N@C80, which wasisolated by high performance liquid chromatography (HPLC). We systematicallystudied the molecular structures and electronic properties of TiSc2N@C80. Ourresults revealed that, the encapsulation of Ti significantly affected the electronicproperties of the outer carbon cage. In specific, the electrochemical property ofTiSc2N@C80 is dramatically different to that of the well known Sc3N@C80 interms of the reversible redox behavior.2. The first Ti-containing non-scandium MMNCF—TiY2N@C80 was successfullysynthesized and isolated, thus expanding the family of the Ti-based metal nitrideclusterfullerenes. We characterized the electronic properties of TiY2N@C80 by aseries of spectroscopic methods, and determined its molecular structure incombination with theoretical calculations. It was found that the reductionpotentials of TiY2N@C80 were obviously negatively shifted compared to those ofTiSc2N@C80, revealing the determinative influence of the encaged group-IIImetal on the electronic property of the Ti-containing MMNCFs.3. By mixing Y/Ti in the raw materials, the first monometallic endohedralmetalloazafullerene (Y@C83N) was successfully synthesized and isolated.Y@C83N represents the third example of the endohedral azafullerenes, and its discovery expanded the family of azafullerenes from C79N to C83N. By spectroscopic characterizations in combination with theoretical calculations, we determined the molecular structure of Y@C83N including the N-substitution site in the carbon cage.4. Several new thio-derivatives of C60 were synthesized by the one-pot Prato reaction, including the unexpected thiazolidine-fulleropyrrolidine. We studied the possible reaction mechanism of thiazolidine-fulleropyrrolidine, revealing that the active hydrogen of S-H in the fulleropyrrolidine was essential for the formation of the thiazolidine ring.