Date of Award

Summer 8-2016

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry and Biochemistry

School

Mathematics and Natural Sciences

Committee Chair

Paige Buchanan

Committee Chair Department

Chemistry and Biochemistry

Committee Member 2

Song Guo

Committee Member 2 Department

Chemistry and Biochemistry

Committee Member 3

Wujian Miao

Committee Member 3 Department

Chemistry and Biochemistry

Committee Member 4

Karl J. Wallace

Committee Member 4 Department

Chemistry and Biochemistry

Committee Member 5

James H. Wynne

Abstract

This work explores the derivatization of C60 and Sc3N@C80 with S-, P-, and C- centered radicals, and is the first exploration into the functionalization of Sc3N@C80 with sulfur and phosphorous. The number of addends bound to C60, as a function of reaction time and molar ratios, as well as, structure-property relationships including thermal stability, solubility, and singlet oxygen generation were explored. Fullerene derivatives exhibiting enhanced solubility were incorporated into two different thiol-ene polymer matrices at varying thiol-ene monomer concentrations (1:1 or 1:0.75 molar equivalents) and at different C60 loadings (0, 1, 5, 10, and 20 wt %). The degree of incorporation and the dispersibility of prepared fullerenes within the thiol-ene matrix and the effect on the thermal and mechanical properties and singlet oxygen generation of the fullerene-containing thiol-ene films as a function of monomer identity and C60 loading was explored, along with the characterization of photooxidized products produced upon generating singlet oxygen.

The ability of C60 to produce singlet oxygen was utilized to prepare a singlet-oxygen generating heterogenous photocatalyst. A series of thiol-ene polymer microbeads (PMBs), containing residual thiols on the surface, were prepared via high-shear suspension photopolymerization, and the thermal, mechanical, and physical properties of the networks, as a function of monomer composition, were explored. PETMP:TTT thiol-ene PMBs possessing the highest Tg (45 °C) and greatest sample uniformity were chosen for derivatization with C60 in a surface thiol-ene reaction to demonstrate the accessibility and reactivity of the residual thiols, the successful inclusion of C60 as the reactive ene moiety, and overall PMB utility as a scaffold for supported photocatalysts.

ORCID ID

0000-0002-6269-869X

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