The electronic structure of Sc3@C82, oxidation of C60 during ethylenediamine addition or through O2 exposure of C60 anions, and intercalation of C60-ethylenediamine derivatives into Alpha-zirconium phosphate /
| Main Author: | |
|---|---|
| Other Authors: | , , |
| Format: | Thesis Book |
| Language: | English |
| Published: |
1994.
|
| Subjects: | |
| Online Access: | Link to OAKTrust Copy Link to ProQuest copy |
| Abstract: | This dissertation contains a number of studies on C$ sb{60}$ and fullerene chemistry. Included is a theoretical study of $ rm Sc sb3 @C sb‚.$ The oxidation behavior of C$ sb{60}$ and its anions is also investigated. Finally, the intercalation of C$ sb{60}$-ethylenediamine derivatives into $ alpha$-zirconium phosphate is presented. Extended Huckel calculations were used to determine the nature of metal fullerene interaction in $ rm Sc sb3 @C sb‚.$ It was found that the placement of the Sc$ sb3$ trimer within the fullerene cage had a pronounced effect on the outcome of the calculations. It was found that a placement 2.5 A above the coronene fragment of C$ sb‚,$ with each Sc slightly off the center of a six membered ring, produced results most consistent with the observed EPR results. At this position, the HOMO was nondegenerate with a$ sb2 sp{ prime prime}$ symmetry and was separated by 0.45 eV from the LUMO. Rotation by 30$ sp circ$ resulted in a smaller HOMO-LUMO gap, while rotation by 60$ sp circ$ produced no significant change in the results. Regardless of the position of the Sc$ sb3$ trimer within the fullerene cage, it was found that metal-fullerene interaction is important in $ rm Sc sb3 @C sb‚$ suggesting that fullerene cages do not comprise inert matrices for the metals that they enclose. The handling of C$ sb{60}$ subsequent to its isolation and purification is an important factor in determining the outcome of its reaction chemistry. It was found that three different types of products can be obtained in the reaction of C$ sb{60}$ with ethylenediamine depending on the amount of oxygen present during the reaction or in the C$ sb{60}$ starting material. True ethylenediamine addition products can be obtained if strict anaerobic conditions are maintained throughout the reaction. The products obtained when oxygen is present are believed to be oxidation products of C$ sb{60}$ such as polyols with hydrogen bonded ethylenediamine or products with both OH's and ethylenediamines added. The water soluble ethylenediamine derivatives of C$ sb{60}$ can be used for further reaction chemistry. Intercalation of these derivatives into $ alpha$-zirconium phosphate leads to layered materials with an interlayer spacing of 35 A and enhanced thermal properties. Multihydroxy addition products of C$ sb{60}$ can also be obtained from oxidation of C$ sb{60}$ anions. Esterification of these fullerols with 4-bromovalleryl chloride was monitored using both IR and $ sp1$H NMR spectroscopies. |
|---|---|
| Item Description: | Vita. "Major subject: Chemistry." In title, symbol for Greek letter Alpha is used and some numerals are subscripts. |
| Physical Description: | xv, 152 leaves : illustrations ; 28 cm |
| Bibliography: | Includes bibliographical references. |