Date of Award


Document Type


Degree Name

Doctor of Philosophy (PhD)

Legacy Department



Smith, Dennis W


Bis-ortho-diynyl arenes (BODA) monomers contain two arenediyne functional groups with variable functionality at both the linker group, X, and the alkyne terminal group, R. These arenediyne moieties undergo thermal Bergman reactions to cycloaromatize to naphthyl diradical species. The inclusion of two of these arenediyne functionalities allows the polymer to grow without losing processability and solubility as most aromatic polymers do. The second functionality acts as a solubilizing group until all functionalities are consumed in the fully cured network polymer.
When heated above 800 °C, BODA polymer converts to a high-yield glassy carbon material. This work has been extended with the fabrication of nano-scale features in a carbon inverse opal photonic crystal consisting of a 3-dimensional periodic array of voids in a carbon matrix. The carbon inverse opal was demonstrated as a sensitive detector element by filling the voids with solvents of differing concentrations, a liquid crystal in the phase change, and buffered hemoglobin solutions.
Disordered porous foam has also been developed that can be used as an electrode material in hydrogen fuel cell MEAs. Bimodal carbon foams of nanoporous foam coating the interior surfaces of a macroporous foam are also demonstrated. Carbon electrode and fluorinated proton exchange membrane compatibility has been addressed by the development of a new carbon surface fluorination technique involving a trifluorovinyl ether containing diazonium salt.
BODA produced radicals have been demonstrated to be capable of direct surface addition reactions to functionalize and solubilize fullerene materials. This is demonstrated with both C60, and the newer carbon nano-onion materials. This is one of the first additions of a conjugated polymer to a C60, and of any polymer to CNOs. The copolymers may have applications in photovoltaic materials.
BODA chemistry has been extended with the complementary technology of mono-ortho-diynyl arene (MODA) monomers. Six MODA monomers consisting of one enediyne group and a functionality have been synthesized and their utility has been demonstrated as a way to increase the chain length between crosslinks in a BODA network; to endcap a functional oligo(aromatic ether sulfone) to produce a BODA macromonomer; and as a route to new BODA monomers.