| This dissertation involves design, synthesis and characterization of organic and polymeric materials.; In chapter 1, non-linear optical (NLO) chromophore containing monomers have been designed and strategies for protecting groups have been developed. These monomers have an amino group on one end and a carboxylic acid functionality on the other. Two series of convergent synthesis were conducted to achieve protected monomers which allow selective, simultaneous, or sequential deprotection to give singly protected or unprotected monomers. Sequential synthesis was performed to yield main-chain NLO oligomers, with well defined lengths. Unprotected monomers were polymerized to give either polyamide or polyurea. These main-chain NLO chromophore containing oligomers and polymers were joined with other polymeric blocks to form block copolymers which are designed for asymmetric self-assembly.; In chapter 2, dihydridocarbonyltris(triphenylphosphine)ruthenium (Ru catalyst) is applied to the synthesis of copolymers containing oligo-thiophene and siloxane units. 1,4-bis(5'-Acetyl-2 '-thienyl)benzene undergoes direct Ru catalyzed reaction with 1,3-divinyltetramethyldisiloxane to give copolymer. On the other hand, 1,3- bis(5'-acetyl-2'-thienyl)benzene was reacted with vinylpentamethyldisiloxane under Ru catalyzed conditions, followed by acid catalyzed equilibration polymerization to give copolymer. Photochemical properties of these materials were studied.; In chapter 3, N-aryl-2,3-dichloromaleimide and N-aryl-2,3-diiodomaleimide monomers were prepared. Dichloro monomers can be polymerized by dechlorination with zinc whereas diiodo monomers undergo thermal polymerization via the elimination of iodine. These polymers are thermally stable cis-polyacetylenes. Photochemical and electrochemical studies were carried out on these materials.; In chapter 4, dihydridocarbonyltris(triphenylphosphine)ruthenium was found to catalyze the homopolymerization of N-alkyl and N-aryl maleimides to yield vinyl polymers. Properties such as solubility and thermal stability of these polymers were studied.; In chapter 5, a photochromic system, which involves N-methyl-2,3-bis(2 '-methyl-5'-phenyl-3'-thienyl)maleimide as one of the two states, was designed. Multi-step synthesis was executed toward the target molecule. This molecular switching system may have unique behavior of photochemical interconversion which is suitable for erasable optical data storage exhibiting nondestructive readout capacity. |
