| Toward the synthesis of new molecular scale electronic materials, new strained unsaturated rings have been synthesized and explored in terms of their reactivity in the context of ROMP, metal catalyzed oligomerization, and as new bulky ligands for organometallic chemistry. In Chapter 2, a new strained unsaturated cyclophane, (5Z, 11E)-dibenzo[a,e]cyclooctatetrene, is introduced. Its structural features and reactivity are analyzed. This new monomer was used to produce a novel poly(o-phenylene vinylene). Details of this polymerization and properties of the polymer product are discussed. In Chapter 3, the reactivity of the known strained medium sized ring, 5,6-didehydrodibenzo[a,e]cyclooctene, is examined. The synthesis and properties of alternating poly(phenylene vinylene)(phenylene ethynylene) from this monomer is discussed. Catalytic oligomerization of this strained alkyne with ruthenium is investigated. In Chapter 4, a large number of unsaturated cyclophanes are explored as potential building blocks. This chapter catalogs synthetic methods and design strategies for synthesizing unsaturated macrocycles. In Chapter 5, (5Z, 11E)-dibenzo[a,e]cyclooctatetrene is examined as a ligand for nickel. The structural characteristics and chemical transformations of these new organometallic complexes are discussed. |
