Synthesis, reactions, and applications of bis-ortho-diynyl arene (BODA) monomers, polymers, and derivatives

This work focuses on the expansion of the scope of processability, reactivity, and synthesis of bis-ortho-diynyl arenes (BODA) monomers. This unique class of monomers consists of molecules that contain two arenediyne functional groups linked together through a variable spacer group X. There is also variable functionality at the alkyne terminal group, R. These arenediyne moieties undergo thermal Bergman reactions to cycloaromatize and form naphthyl diradical species. The inclusion of two of these arenediyne functionalities allows the polymer to grow without losing processability and solubility as most aromatic polymer do. The second functionality acts as a solubilizing group until all functionalities are consumed in the fully cured network polymer.; BODA polymers were initially developed as processable high-yield carbon precursors. When heated above 800°C, the polymer converts to a glassy carbon material. This work has been extended with the fabrication of nano-scale features in a carbon inverse opal photonic crystal. The carbon inverse opal structure consists of 3-dimensionally alternating carbon and voids. The wavelength excluded depends on both the fixed scale of the periodicity and the dielectric contrast between the carbon and the voids. This has been demonstrated by using the carbon inverse opal as a sensitive detector element by filling the voids with solvents to detect concentrations, the liquid crystal 5CB to detect the phase change, and hemoglobin in buffered solutions.; Disordered porous foam has also been developed for use as an electrode material in H2 fuel cell MEAs. The pore size and surface area are examined as a function of BODA monomer functionality. Bimodal carbon foams that consist of nanoporous foam coating the interior surfaces of a macroporous foam are also demonstrated. Compatibility between the carbon electrode and fluorinated proton exchange membrane 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. The copolymers thus produced are examined by TEM, Raman, TGA, MALDI-TOF MS, GPC, MALLS, and solubility tests. 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. These monomers consist of one enediyne group and a functional group on the ring. Six MODA monomers have been synthesized and their utility has been demonstrated as a way to increase the chain length between crosslinks in a BODA network, a way to endcap a functional oligomer to produce a BODA macromonomer as demonstrated with the endcapping of a poly(aromatic ether sulfone), and as a route to new previously unattainable BODA monomers, as demonstrated with a fluorescent monomer.