Date of Award

12-2010

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Legacy Department

Chemistry

Committee Chair/Advisor

Creager, Stephen E

Committee Member

Dieter , Karl

Committee Member

Smith , Rhett C

Committee Member

Hwu , Shiou-Jyh

Committee Member

Echegoyen , Luis

Abstract

The preparation and electrochemical properties of donor - acceptor systems based on trimetallic nitride endohedral metallofullerenes (TNT-EMFs) for enhanced solar energy conversion is described. It was found that TNT-EMFs have an enhanced ability to stabilize charge separated states formed upon light irradiation when compared to empty cage fullerene analogues. The influence of the linker connecting the donor and acceptor moieties was studied in two different systems. Optimal conditions for preparing cyclopropanated Bingel-Hirsch derivaties of the most common TNT-EMFs were found; this functionalization approach is a very useful alternative to the 1,3-dipolar cycloaddition reactions that yield pyrrolidine derivatives, because the latter are sensitive to both heat and oxidation.
Novel D-A systems were prepared using this strategy and their electrochemical properties revealed that they form films by electro-oxidative polymerization. These films generate current under irradiation. Finally, the arcing conditions for the preparation of a novel sulfur endohedral metallofullerene family were optimized and their electrochemical properties were studied. Due to the high yields obtained, these new endohedral compounds may also be potential candidates to be used in similar applications to those found for other TNT-EMFs.

Included in

Chemistry Commons

Share

COinS
 
 

To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.